Sample records for quartz manganese oxide

  1. Tellurium content of marine manganese oxides and other manganese oxides

    USGS Publications Warehouse

    Lakin, H.W.; Thompson, C.E.; Davidson, D.F.

    1963-01-01

    Tellurium in amounts ranging from 5 to 125 parts per million was present in all of 12 samples of manganese oxide nodules from the floor of the Pacific and Indian oceans. These samples represent the first recognized points of high tellurium concentration in a sedimentary cycle. The analyses may lend support to the theory that the minor-element content of seafloor manganese nodules is derived from volcanic emanations.

  2. Manganese oxide cathodes for rechargeable batteries

    Microsoft Academic Search

    Dongmin Im

    2002-01-01

    Manganese oxides are considered as promising cathodes for rechargeable batteries due to their low cost and low toxicity as well as the abundant natural resources. In this dissertation, manganese oxides have been investigated as cathodes for both rechargeable lithium and alkaline batteries. Nanostructured lithium manganese oxides designed for rechargeable lithium cells have been synthesized by reducing lithium permanganate with methanol

  3. OXIDATION AND SORPTION KINETICS OF ARSENIC ON A POORLY CRYSTALLINE MANGANESE OXIDE

    E-print Network

    Sparks, Donald L.

    OXIDATION AND SORPTION KINETICS OF ARSENIC ON A POORLY CRYSTALLINE MANGANESE OXIDE by Brandon J MANGANESE OXIDE by Brandon J. Lafferty Approved..........................................................................................................1 Manganese Oxides...................................

  4. Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide. 2.

    E-print Network

    Sparks, Donald L.

    Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide. 2. Results from X-ray Absorption September 23, 2010. Accepted October 1, 2010. Arsenite (AsIII ) oxidation by manganese oxides (Mn Manganese-oxides (Mn-oxides) commonly occur as fine- grained particles or coatings in terrestrial

  5. Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide 1.

    E-print Network

    Sparks, Donald L.

    Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide 1. Stirred-Flow Experiments B R A N D O September 23, 2010. Accepted October 1, 2010. Manganese-oxides (Mn-oxides) are quite reactive, with respect of studying reaction mechanisms over time. Introduction Manganese-oxide minerals (Mn-oxides) are powerful

  6. Manganese oxidation by Leptothrix discophora.

    PubMed Central

    Boogerd, F C; de Vrind, J P

    1987-01-01

    Cells of Leptothrix discophora SS1 released Mn2+-oxidizing factors into the medium during growth in batch culture. Manganese was optimally oxidized when the medium was buffered with HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid) at pH 7.5. Manganese-oxidizing activity in the culture medium in which this strain had been grown previously was sensitive to heat, phosphate, Tris, NaN3, HgCl2 NaCl, sodium dodecyl sulfate, and pronase; 0.5 mol of O2 was consumed per mol of MnO2 formed. During Mn2+ oxidation, protons were liberated. With sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two protein-containing bands were detected in the spent culture medium. One band had an apparent molecular weight of 110,000 and was predominant in Mn2+-oxidizing activity. The second product (Mr 85,000) was only detected in some cases and probably represents a proteolytic breakdown moiety of the 110,000-Mr protein. The Mn2+-oxidizing factors were associated with the MnO2 aggregates that had been formed in spent culture medium. After solubilization of this MnO2 with ascorbate, Mn2+-oxidizing activity could be recovered. Images PMID:3804969

  7. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 false Barium calcium manganese strontium oxide. 721.10011 Section...Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance...substance identified as barium calcium manganese strontium oxide (PMN...

  8. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 false Barium calcium manganese strontium oxide. 721.10011 Section...Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance...substance identified as barium calcium manganese strontium oxide (PMN...

  9. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 false Barium calcium manganese strontium oxide. 721.10011 Section...Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance...substance identified as barium calcium manganese strontium oxide (PMN...

  10. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 false Barium calcium manganese strontium oxide. 721.10011 Section...Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance...substance identified as barium calcium manganese strontium oxide (PMN...

  11. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...false Cobalt lithium manganese nickel oxide. 721.10201 Section...10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance...as cobalt lithium manganese nickel oxide (PMN P-04-269...Requirements as specified in § 721.63 (a)(1),...

  12. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...false Cobalt lithium manganese nickel oxide. 721.10201 Section...10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance...as cobalt lithium manganese nickel oxide (PMN P-04-269...Requirements as specified in § 721.63 (a)(1),...

  13. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...false Cobalt lithium manganese nickel oxide. 721.10201 Section...10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance...as cobalt lithium manganese nickel oxide (PMN P-04-269...Requirements as specified in § 721.63 (a)(1),...

  14. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Barium calcium manganese strontium oxide. 721.10011...Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a...chemical substance identified as barium calcium manganese strontium oxide (PMN...

  15. Synthesis, characterization, optical and sensing property of manganese oxide nanoparticles

    SciTech Connect

    Manigandan, R.; Suresh, R.; Giribabu, K.; Narayanan, V., E-mail: vnnara@yahoo.co.in [Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai 600 025 (India); Vijayalakshmi, L. [Annai Veilankanni's College for Women (Arts and Science), Saidapet, Chennai 600015 (India); Stephen, A. [Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai 600 025 (India)

    2014-01-28

    Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

  16. Synthesis, characterization, optical and sensing property of manganese oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Manigandan, R.; Suresh, R.; Giribabu, K.; Vijayalakshmi, L.; Stephen, A.; Narayanan, V.

    2014-01-01

    Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

  17. Kinetic Modeling of Oxidation of Antibacterial Agents by Manganese

    E-print Network

    Huang, Ching-Hua

    Kinetic Modeling of Oxidation of Antibacterial Agents by Manganese Oxide H U I C H U N Z H A N G demonstratedinearlierstudiestobehighlysusceptibletooxidation by manganese oxides, a common oxidant in soils. However, because of the high complexity of oxidative transformation of organic contaminants by manganese oxides in well-defined systems. Introduction

  18. The Products of Manganese (II) Oxidation

    SciTech Connect

    Perkins, A.

    2004-09-03

    Manganese, the second most abundant transition metal in the earth's crust, exists in a number of oxidation states, among which the II, III, and IV oxidation states are of greatest environmental importance. Produced through microbial activity, manganese oxides help to mediate redox reactions with organic and inorganic compounds and help to sequester a variety of metals. The mechanism by which Manganese (II) is oxidized to Manganese (IV) is a biologically catalyzed process. There are at least three different pathways by which Mn(II) can be bacterially oxidized to Mn(IV); the first in which states that Mn(II) can be oxidized to mixed Mn(III, IV), and Mn(IV) oxides and oxyhydroxides. The second of these pathways is that Mn(II) can be directly oxidized to Mn(IV) and the last of these pathways is that Mn(II) follows an enzymatic bond with a Mn(III) intermediate in which Mn(II) oxidizes to Mn(III) and then to Mn(IV). The pathways of focus for this research are the latter two pathways.

  19. Silver manganese oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2006-05-09

    This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

  20. Directed Vapor Deposition of Lithium Manganese Oxide Films

    E-print Network

    Wadley, Haydn

    Directed Vapor Deposition of Lithium Manganese Oxide Films A Dissertation Presented to the faculty the deposition of lithium manganese oxide films. Many phases with offering various electrochemical performance techniques. As-deposited lithium manganese oxide films grown on substrates at ambient temperature using high

  1. Pwave Pairing and Colossal Magnetoresistance in Manganese Oxides

    E-print Network

    P­wave Pairing and Colossal Magnetoresistance in Manganese Oxides Yong­Jihn Kim y Department that the existing experimental data of most manganese ox­ ides show the frustrated p­wave superconducting paid to the manganese oxides since the observa­ tion of colossal magnetoresistance (CMR). 1\\Gamma4

  2. Manganese oxide cathodes for rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Im, Dongmin

    Manganese oxides are considered as promising cathodes for rechargeable batteries due to their low cost and low toxicity as well as the abundant natural resources. In this dissertation, manganese oxides have been investigated as cathodes for both rechargeable lithium and alkaline batteries. Nanostructured lithium manganese oxides designed for rechargeable lithium cells have been synthesized by reducing lithium permanganate with methanol or hydrogen in various solvents followed by firing at moderate temperatures. The samples have been characterized by wet-chemical analyses, thermal methods, spectroscopic methods, and electron microscopy. It has been found that chemical residues in the oxides such as carboxylates and hydroxyl groups, which could be controlled by varying the reaction medium, reducing agents, and additives, make a significant influence on the electrochemical properties. The Li/Mn ratio in the material has also been found to be a critical factor in determining the rechargeability of the cathodes. The optimized samples exhibit a high capacity of close to 300 mAh/g with good cyclability and charge efficiency. The high capacity with a lower discharge voltage may make these nanostructured oxides particularly attractive for lithium polymer batteries. The research on the manganese oxide cathodes for alkaline batteries is focused on an analysis of the reaction products generated during the charge/discharge processes or by some designed chemical reactions mimicking the electrochemical processes. The factors influencing the formation of Mn3O4 in the two-electron redox process of delta-MnO2 have been studied with linear sweep voltammetry combined with X-ray diffraction. The presence of bismuth, the discharge rate, and the microstructure of the electrodes are found to affect the formation of Mn3O4, which is known to be electrochemically inactive. A faster voltage sweep and a more intimate mixing of the manganese oxide and carbon in the cathode are found to suppress the formation of Mn3O4. Bismuth has also been found to be beneficial in the one-electron process of gamma-MnO 2 when incorporated into the cathode. The results of a series of chemical reactions reveal that bismuth is blocking some reaction paths leading to the unwanted birnessite or Mn3O4. Barium is also found to play a similar role, but it is less effective than bismuth for the same amount of additive. Optimization of the additives has the potential to make the rechargeable alkaline cells based on manganese oxides to successfully compete with other rechargeable systems due to their low cost, environmental friendliness, and excellent safety features.

  3. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    E-print Network

    Huang, Ching-Hua

    Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide Wan-Ru Chen 1 tetracyclines. Ã? 2011 Elsevier Ltd. All rights reserved. 1. Introduction Manganese, commonly present as Mn

  4. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  5. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 2014-07-01 false Cobalt iron manganese oxide, carboxylic acid-modified...Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid-modified...identified generically as cobalt iron manganese oxide, carboxylic...

  6. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 2013-07-01 false Cobalt iron manganese oxide, carboxylic acid-modified...Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid-modified...identified generically as cobalt iron manganese oxide, carboxylic...

  7. 75 FR 70665 - Proposed Significant New Use Rule for Cobalt Lithium Manganese Nickel Oxide

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-18

    ...Proposed Significant New Use Rule for Cobalt Lithium Manganese Nickel Oxide AGENCY...for the chemical substance identified as cobalt lithium manganese nickel oxide (CAS No...for the chemical substance identified as cobalt lithium manganese nickel oxide...

  8. Manganese oxide nanowires, films, and membranes and methods of making

    DOEpatents

    Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

    2011-02-15

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

  9. Biological Superoxide In Manganese Oxide Formation

    NASA Astrophysics Data System (ADS)

    Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

    2011-12-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

  10. Electrochromic reactions in manganese oxides I. Raman analysis

    SciTech Connect

    Bernard, M.C.; Hugot-Le Goff, A.; Thi, B.V. (Univ. Pierre et Marie Curie, Paris (France). UPR 15 du CNRS Physique des Liquides et Electrochimie); Cordoba de Torresi, S. (Univ. Estadual de Campinas (Brazil). Dept. de Fisica Aplicada)

    1993-11-01

    Like nickel oxide, manganese oxide is a widely studied material in the primary batteries field. The reactions taking place during voltametric cycling of manganese oxides can be determined using in situ Raman spectroscopy. The main difficulty for the oxide identification is to obtain relevant Raman reference spectra because of the many possible compounds and, for some of these compounds, of their instability in the laser beam. As a consequence, several modifications of different tetra-, tri- and divalent manganese oxides and oxyhydroxides were carefully studied. The electrochromic behavior of three types of manganese oxides, two prepared by thermal oxidations and the other by electrochemical deposition, were then compared. The presence of nonstoichiometry in the pristine material was necessary to obtain a reversible electrochromic effect. The reaction during electrochromic cycling is more complicated than a simple passage from MnO[sub 2] to MnOOH.

  11. Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

  12. Arsenic mobilization in the critical zone: Oxidation by hydrous manganese oxide Jason S. Fischel, fischjs06@juniata.edu1

    E-print Network

    Sparks, Donald L.

    Arsenic mobilization in the critical zone: Oxidation by hydrous manganese oxide GEOC 112 Jason S manganese (Mn) oxides, even in low concentrations, to oxidize trace metals such as arsenic from arsenite [As

  13. Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria.

    PubMed

    Vandieken, Verona; Pester, Michael; Finke, Niko; Hyun, Jung-Ho; Friedrich, Michael W; Loy, Alexander; Thamdrup, Bo

    2012-11-01

    Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the prevailing terminal electron-accepting process in anoxic incubations of surface sediments, and even the addition of acetate stimulated neither iron nor sulfate reduction. The three geographically distinct sediments harbored surprisingly similar communities of acetate-utilizing manganese-reducing bacteria: 16S rRNA of members of the genera Colwellia and Arcobacter and of novel genera within the Oceanospirillaceae and Alteromonadales were detected in heavy RNA-SIP fractions from these three sediments. Most probable number (MPN) analysis yielded up to 10(6) acetate-utilizing manganese-reducing cells cm(-3) in Gullmar Fjord sediment. A 16S rRNA gene clone library that was established from the highest MPN dilutions was dominated by sequences of Colwellia and Arcobacter species and members of the Oceanospirillaceae, supporting the obtained RNA-SIP results. In conclusion, these findings strongly suggest that (i) acetate-dependent manganese reduction in manganese oxide-rich sediments is catalyzed by members of taxa (Arcobacter, Colwellia and Oceanospirillaceae) previously not known to possess this physiological function, (ii) similar acetate-utilizing manganese reducers thrive in geographically distinct regions and (iii) the identified manganese reducers differ greatly from the extensively explored iron reducers in marine sediments. PMID:22572639

  14. Carbothermal Reduction of Manganese Oxide in Different Gas Atmospheres

    Microsoft Academic Search

    Ring Kononov; Oleg Ostrovski; Samir Ganguly

    2008-01-01

    Carbothermal reduction of manganese oxides was studied in hydrogen, helium, and argon at different temperatures and carbon-to-manganese\\u000a oxide ratios. Isothermal and temperature programmed carbothermal reduction experiments were conducted in a fixed bed reactor\\u000a in a vertical tube furnace, with on-line monitoring of gas composition by the CO-CO2 infrared sensor. The extent of reduction was calculated using the off-gas composition and

  15. Manganese and Oxidative Damage in Cucumber

    Microsoft Academic Search

    Rajeev Gopal

    2008-01-01

    Micronutrients in low or high concentration can affect growth, respiration, photosynthesis, and reproduction in plants. Cucumber (Cucumis sativus, L.) is grown in India in areas low or high in manganese concentration in soils. A study was conducted to investigate the effects of manganese concentration on some metabolic activities affecting developmental responses in cucumber. Seed of cucumber, cv. Sonali, were grown

  16. Nano-sized layered aluminium or zinc-manganese oxides as efficient water oxidizing catalysts.

    PubMed

    Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

    2012-06-21

    Nano-sized layered aluminium or zinc-manganese oxides were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, dynamic light scattering and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. Amounts of dissolved manganese, zinc or aluminium, and water oxidation activities of these oxides were reported and compared with other manganese oxides. A mechanism for oxygen evolution and possible roles for zinc or aluminium ions are also proposed. PMID:22565665

  17. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    E-print Network

    Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water

  18. The Molecular Geomicrobiology of Bacterial Manganese(II) Oxidation

    Microsoft Academic Search

    Bradley M. Tebo; Kati Geszvain; Sung-Woo Lee

    \\u000a Manganese is the second most abundant transition metal found in the Earth’s crust. It has a significant biological role as\\u000a it is a cofactor of enzymes such as superoxide dismutase and is the key metal in the reaction center of photosystem II. In\\u000a the environment, manganese is mostly found in three different oxidation states: II, III, and IV. Mn(II), primarily

  19. Giant negative magnetoresistance in Manganese-substituted Zinc Oxide

    PubMed Central

    Wang, X. L.; Shao, Q.; Zhuravlyova, A.; He, M.; Yi, Y.; Lortz, R.; Wang, J. N.; Ruotolo, A.

    2015-01-01

    We report a large negative magnetoresistance in Manganese-substituted Zinc Oxide thin films. This anomalous effect was found to appear in oxygen-deficient films and to increase with the concentration of Manganese. By combining magnetoresistive measurements with magneto-photoluminescence, we demonstrate that the effect can be explained as the result of a magnetically induced transition from hopping to band conduction where the activation energy is caused by the sp-d exchange interaction. PMID:25783664

  20. Giant negative magnetoresistance in Manganese-substituted Zinc Oxide

    NASA Astrophysics Data System (ADS)

    Wang, X. L.; Shao, Q.; Zhuravlyova, A.; He, M.; Yi, Y.; Lortz, R.; Wang, J. N.; Ruotolo, A.

    2015-03-01

    We report a large negative magnetoresistance in Manganese-substituted Zinc Oxide thin films. This anomalous effect was found to appear in oxygen-deficient films and to increase with the concentration of Manganese. By combining magnetoresistive measurements with magneto-photoluminescence, we demonstrate that the effect can be explained as the result of a magnetically induced transition from hopping to band conduction where the activation energy is caused by the sp-d exchange interaction.

  1. Manganese?oxidizing bacteria mediate the degradation of 17??ethinylestradiol

    PubMed Central

    Sabirova, Julia S.; Cloetens, L. F. F.; Vanhaecke, L.; Forrez, I.; Verstraete, Willy; Boon, N.

    2008-01-01

    Summary Manganese (II) and manganese?oxidizing bacteria were used as an efficient biological system for the degradation of the xenoestrogen 17??ethinylestradiol (EE2) at trace concentrations. Mn2+?derived higher oxidation states of Mn (Mn3+, Mn4+) by Mn2+?oxidizing bacteria mediate the oxidative cleavage of the polycyclic target compound EE2. The presence of manganese (II) was found to be essential for the degradation of EE2 by Leptothrix discophora, Pseudomonas putida MB1, P.?putida MB6 and P.?putida MB29. Mn2+?dependent degradation of EE2 was found to be a slow process, which requires multi?fold excess of Mn2+ and occurs in the late stationary phase of growth, implying a chemical process taking place. EE2?derived degradation products were shown to no longer exhibit undesirable estrogenic activity. PMID:21261871

  2. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    NASA Astrophysics Data System (ADS)

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-01

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol-gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated.

  3. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  4. Water defluoridation by aluminium oxide-manganese oxide composite material.

    PubMed

    Alemu, Sheta; Mulugeta, Eyobel; Zewge, Feleke; Chandravanshi, Bhagwan Singh

    2014-08-01

    In this study, aluminium oxide-manganese oxide (AOMO) composite material was synthesized, characterized, and tested for fluoride removal in batch experiments. AOMO was prepared from manganese(II) chloride and aluminium hydroxide. The surface area of AOMO was found to be 30.7m2/g and its specific density was determined as 2.78 g/cm3. Detailed investigation of the adsorbent by inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry, and ion chromatography (for sulphate only) showed that it is composed of Al, Mn, SO4, and Na as major components and Fe, Si, Ca, and Mg as minor components. Thermogravimetric analysis was used to study the thermal behaviour of AOMO. X-ray diffraction analysis showed that the adsorbent is poorly crystalline. The point of zero charge was determined as 9.54. Batch experiments (by varying the proportion of MnO, adsorbent dose, contact time, initial F concentration, and raw water pH) showed that fluoride removal efficiency ofAOMO varied significantly with percentage of MnO with an optimum value of about I11% of manganese oxide in the adsorbent. The optimum dose of the adsorbent was 4 g/L which corresponds to the equilibrium adsorption capacity of 4.8 mg F-/g. Both the removal efficiency and adsorption capacity showed an increasing trend with an increase in initial fluoride concentration of the water. The pH for optimum fluoride removal was found to be in the range between 5 and 7. The adsorption data were analysed using the Freundlich, Langmuir, and Dubinirn-Radushkevich models. The minimum adsorption capacity obtained from the non-linear Freundlich isotherm model was 4.94 mg F-/g and the maximum capacity from the Langmuir isotherm method was 19.2mg F-/g. The experimental data of fluoride adsorption on AOMO fitted well to the Freundlich isotherm model. Kinetic studies showed that the adsorption is well described by a non-linear pseudo-second-order reaction model with an average rate constant of 3.1 x 10(-2) g/min mg. It is concluded that AOMO is a highly promising adsorbent for the removal of excess fluoride from drinking water. PMID:24956783

  5. Manganese- and iron-dependent marine methane oxidation.

    PubMed

    Beal, Emily J; House, Christopher H; Orphan, Victoria J

    2009-07-10

    Anaerobic methanotrophs help regulate Earth's climate and may have been an important part of the microbial ecosystem on the early Earth. The anaerobic oxidation of methane (AOM) is often thought of as a sulfate-dependent process, despite the fact that other electron acceptors are more energetically favorable. Here, we show that microorganisms from marine methane-seep sediment in the Eel River Basin in California are capable of using manganese (birnessite) and iron (ferrihydrite) to oxidize methane, revealing that marine AOM is coupled, either directly or indirectly, to a larger variety of oxidants than previously thought. Large amounts of manganese and iron are provided to oceans from rivers, indicating that manganese- and iron-dependent AOM have the potential to be globally important. PMID:19589998

  6. Manganese- and Iron-Dependent Marine Methane Oxidation

    NASA Astrophysics Data System (ADS)

    Beal, Emily J.; House, Christopher H.; Orphan, Victoria J.

    2009-07-01

    Anaerobic methanotrophs help regulate Earth’s climate and may have been an important part of the microbial ecosystem on the early Earth. The anaerobic oxidation of methane (AOM) is often thought of as a sulfate-dependent process, despite the fact that other electron acceptors are more energetically favorable. Here, we show that microorganisms from marine methane-seep sediment in the Eel River Basin in California are capable of using manganese (birnessite) and iron (ferrihydrite) to oxidize methane, revealing that marine AOM is coupled, either directly or indirectly, to a larger variety of oxidants than previously thought. Large amounts of manganese and iron are provided to oceans from rivers, indicating that manganese- and iron-dependent AOM have the potential to be globally important.

  7. Electron Energy-Loss Safe-Dose Limits for Manganese Valence Measurements in Environmentally Relevant Manganese Oxides

    E-print Network

    Sparks, Donald L.

    Relevant Manganese Oxides Kenneth J. T. Livi,*, Brandon Lafferty,,§ Mengqiang Zhu,,# Shouliang Zhang, Anne-Claire Gaillot, and Donald L. Sparks The High-Resolution Analytical Electron Microbeam Facility Houssiniere, BP 32229, 44322 Nantes Cedex 3, France *S Supporting Information ABSTRACT: Manganese (Mn) oxides

  8. Biochemical changes in pulmonary cells following manganese oxide inhalation

    SciTech Connect

    Adkins, B. Jr. (Northrop Services, Inc., Research Triangle Park, NC); Luginbuhl, G.H.; Gardner, D.E.

    1980-03-01

    Inhalation of manganese oxide (Mn dose, 879.0 ..mu..g/m/sup 3/) for 2 h reduced the total number of alveolar macrophages obtained by endotracheal lavage in pulmonary cell populations, slightly reduced cellular viability, and reduced both phagocytic capability and total protein in sonicated pulmonary cells. Increases in intracellular adenosine triphosphate and acid phosphatase specific activity were also exhibited by the pulmonary cells, but sonicated cells obtained from the exposed mice showed no change in lactic acid dehydrogenase specific activity. A slight increase in extracellular protein in the fluid phase of the lavage suspension was observed after manganese oxide exposure.

  9. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Lithium manganese oxide (LiMn204) (generic name...Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name...substance identified generically as lithium manganese oxide (LiMn204)...

  10. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Barium manganese oxide (BaMnO3). 721.10010 Section...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical...chemical substance identified as barium manganese oxide (BaMnO3 ) (PMN...

  11. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Manganese strontium oxide (MnSrO3). 721...Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3 ). ...The chemical substance identified as manganese strontium oxide (MnSrO3 )...

  12. Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides

    E-print Network

    Haskel, Daniel

    Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides B edge X-ray absorption spectra of manganese oxides at the Mn L2,3, Mn K, and O K edges to investigate The particularly rich redox chemistry of manganese is evident in its oxides, which are of wide contemporary

  13. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Manganese strontium oxide (MnSrO3). 721...Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a...The chemical substance identified as manganese strontium oxide (MnSrO3 )...

  14. Lithium manganese oxide films fabricated by electron beam directed vapor deposition

    E-print Network

    Wadley, Haydn

    Lithium manganese oxide films fabricated by electron beam directed vapor deposition S. W. Jina 2007; published 17 December 2007 Lithium manganese oxide thin films have been grown using a gas jet of this material by sputtering and other vapor deposition techniques. The lithium manganese oxide films grown

  15. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Manganese strontium oxide (MnSrO3). 721...Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3 ). ...The chemical substance identified as manganese strontium oxide (MnSrO3 )...

  16. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Barium manganese oxide (BaMnO3). 721.10010 Section...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3 ). (a) Chemical...chemical substance identified as barium manganese oxide (BaMnO3 ) (PMN...

  17. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Barium manganese oxide (BaMnO3). 721.10010 Section...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3 ). (a) Chemical...chemical substance identified as barium manganese oxide (BaMnO3 ) (PMN...

  18. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Lithium manganese oxide (LiMn204) (generic name...Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name...substance identified generically as lithium manganese oxide (LiMn204)...

  19. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721.10010 Section...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical...chemical substance identified as barium manganese oxide (BaMnO3 ) (PMN...

  20. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Barium manganese oxide (BaMnO3). 721.10010 Section...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3 ). (a) Chemical...chemical substance identified as barium manganese oxide (BaMnO3 ) (PMN...

  1. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Lithium manganese oxide (LiMn204) (generic name...Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name...substance identified generically as lithium manganese oxide (LiMn204)...

  2. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Lithium manganese oxide (LiMn204) (generic name...Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name...substance identified generically as lithium manganese oxide (LiMn204)...

  3. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Manganese strontium oxide (MnSrO3). 721...Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3 ). ...The chemical substance identified as manganese strontium oxide (MnSrO3 )...

  4. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Lithium manganese oxide (LiMn204) (generic name...Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name...substance identified generically as lithium manganese oxide (LiMn204)...

  5. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Manganese yttrium oxide (MnYO3). 721.10009 Section...Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance...chemical substance identified as manganese yttrium oxide (MnYO3 ) (PMN...

  6. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Manganese yttrium oxide (Mn2YO5). 721.10013 Section...Substances § 721.10013 Manganese yttrium oxide (Mn2 YO5 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (Mn2 YO5 ) (PMN...

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Manganese yttrium oxide (MnYO3). 721.10009 Section...Substances § 721.10009 Manganese yttrium oxide (MnYO3 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (MnYO3 ) (PMN...

  8. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Manganese yttrium oxide (Mn2YO5). 721.10013 Section...Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance...chemical substance identified as manganese yttrium oxide (Mn2 YO5 ) (PMN...

  9. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Manganese yttrium oxide (Mn2YO5). 721.10013 Section...Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance...chemical substance identified as manganese yttrium oxide (Mn2 YO5 ) (PMN...

  10. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Manganese yttrium oxide (Mn2YO5). 721.10013 Section...Substances § 721.10013 Manganese yttrium oxide (Mn2 YO5 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (Mn2 YO5 ) (PMN...

  11. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Manganese yttrium oxide (MnYO3). 721.10009 Section...Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance...chemical substance identified as manganese yttrium oxide (MnYO3 ) (PMN...

  12. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Manganese yttrium oxide (MnYO3). 721.10009 Section...Substances § 721.10009 Manganese yttrium oxide (MnYO3 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (MnYO3 ) (PMN...

  13. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Manganese yttrium oxide (Mn2YO5). 721.10013 Section...Substances § 721.10013 Manganese yttrium oxide (Mn2 YO5 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (Mn2 YO5 ) (PMN...

  14. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Manganese yttrium oxide (MnYO3). 721.10009 Section...Substances § 721.10009 Manganese yttrium oxide (MnYO3 ). (a) Chemical...chemical substance identified as manganese yttrium oxide (MnYO3 ) (PMN...

  15. 75 FR 70583 - Cobalt Lithium Manganese Nickel Oxide; Withdrawal of Significant New Use Rule

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-18

    ...EPA-HQ-OPPT-2009-0922; FRL-8853-2] RIN 2070-AB27 Cobalt Lithium Manganese Nickel Oxide; Withdrawal...for the chemical substance identified as cobalt lithium manganese nickel oxide (CAS No...EPA is withdrawing the rule issued for cobalt lithium manganese nickel oxide (PMN...

  16. 76 FR 47996 - Cobalt Lithium Manganese Nickel Oxide; Significant New Use Rule

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-08

    ...EPA-HQ-OPPT-2009-0922; FRL-8878-2] RIN 2070-AB27 Cobalt Lithium Manganese Nickel Oxide; Significant...for the chemical substance identified as cobalt lithium manganese nickel oxide (CAS No...for the chemical substance identified as cobalt lithium manganese nickel oxide...

  17. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 2010-07-01 false Manganese strontium oxide (MnSrO3). 721.10008 Section...Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical...chemical substance identified as manganese strontium oxide (MnSrO3 ) (PMN...

  18. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    Microsoft Academic Search

    Judson W. Harvey; Christopher C. Fuller

    1998-01-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport

  19. ENVR Dionysios Dionysiou Wednesday, August 22, 2012 261 -Arsenic mobilization in the critical zone: Oxidation by manganese oxide minerals

    E-print Network

    Sparks, Donald L.

    : Oxidation by manganese oxide minerals Jason S. Fischel1, fischelj@udel.edu, Matthew H. Fischel1, Brandon J Center, U.S. Army Corps of Engineers, Vicksburg, MS 39180, United States Manganese(IV) oxides are one of the main redox catalysts in the subsurface environment. Their highly reactive surfaces allow manganese (Mn

  20. Manganese-oxidizing photosynthesis before the rise of cyanobacteria

    E-print Network

    Fischer, Woodward

    Manganese-oxidizing photosynthesis before the rise of cyanobacteria Jena E. Johnsona,1 , Samuel M) The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however biological innovation-- the evolution of oxygenic photosynthesis (3, 4). Several bio- chemical attributes

  1. Observation of ferromagnetic semiconductor behavior in manganese-oxide doped graphene

    NASA Astrophysics Data System (ADS)

    Park, Chang-Soo; Zhao, Yu; Shon, Yoon; Yoon, Chong S.; Lee, Haigun; Lee, Cheol Jin

    2014-08-01

    We have doped manganese-oxide onto graphene by an electrochemical method. Graphene showed a clear ferromagnetic semiconductor behavior after doping of manganese-oxide. The manganese-oxide doped graphene has a coercive field (Hc) of 232 Oe at 10 K, and has the Curie temperature of 270 K from the temperature-dependent resistivity using transport measurement system. The ferromagnetism of manganese-oxide doped graphene attributes to the double-exchange from the coexistence of Mn3+ and Mn4+ on the surface of graphene. In addition, the semiconducting behavior is caused by the formation of manganese-oxide on graphene.

  2. Arsenic transport and partitioning within manganese- and iron-oxide rich aggregated sediments

    NASA Astrophysics Data System (ADS)

    Ying, S. C.; Masue-Slowey, Y.; Fendorf, S. E.

    2009-12-01

    Manganese and iron oxides are ubiquitous phases in terrestrial environments that have high sorptive capacities for arsenic. Although numerous studies have characterized the effects of As adsorption onto Fe and Mn oxides individually, the fate of arsenic within mixed (competitive) systems representative of natural environments is unresolved. Here, we investigate As dynamics in an aerobic aggregate composed of ferrihydrite and birnessite coated quartz sand fused by an agarose polymer. Mn and Fe oxide coated sands, having pre-adsorbed As(V), are cast into cohesive spheres and inoculated with Shewanella sp. ANA-3, a bacterial strain capable of reducing As(V) and Mn(IV) and Fe(III) oxides. Arsenic(III) produced by bacterial reduction of As(V) within the aggregate diffuses to the aggregate exterior (proximal to aerated solutes), where it is re-oxidized to As(V) by Mn-oxides; following oxidation, As(V) is repartitioned onto the Fe oxides. X-ray fluorescence microprobe analysis was used to map the spatial distribution of As(III) and As(V) within the aggregate, after which ?-XANES was used to confirm arsenic oxidation state within the mapped areas. These results illustrate the dynamic interplay of biogeochemical transformation, physical heterogeneity, and mixed mineralogy representative of field systems on the fate of arsenic.

  3. Kinetics of manganese adsorption, desorption, and oxidation in coastal marine sediments

    E-print Network

    Beaudoin, Georges

    Kinetics of manganese adsorption, desorption, and oxidation in coastal marine sediments Dominique´bec a` Rimouski, Que´bec, Canada Abstract Ejection of excavated manganese (Mn)-laden particles from disturbances triggers desorption and oxidation of reduced manganese species. These competing reactions

  4. Nanoscale manganese oxide within Faujasite zeolite as an efficient and biomimetic water oxidizing catalyst.

    PubMed

    Najafpour, Mohammad Mahdi; Pashaei, Babak

    2012-09-14

    Nanoscale manganese oxides within Faujasite zeolite have been synthesized with a simple method and characterized by scanning electron microscopy, X-ray diffraction spectrometry, N(2) adsorption-desorption isotherms, transmission electron microscopy, and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. PMID:22833185

  5. Manganese oxidation state mediates toxicity in PC12 cells

    SciTech Connect

    Reaney, S.H. [Department of Chemistry and Biochemistry, University of California, Santa Cruz, CA 95064 (United States) and Department of Environmental Toxicology, University of California, 1156 High St., Santa Cruz, CA 95064 (United States)]. E-mail: stevereaney@hotmail.com; Smith, D.R. [Department of Environmental Toxicology, University of California, 1156 High St., Santa Cruz, CA 95064 (United States)

    2005-06-15

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 {mu}M Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 {mu}M produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 {mu}M), while Mn(III) exposures produced increases in LDH activity at lower exposures ({>=}50 {mu}M) than did Mn(II) (200 {mu}M only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 {mu}M Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity.

  6. Thin film passivation of laser generated 3D micro patterns in lithium manganese oxide cathodes

    NASA Astrophysics Data System (ADS)

    Pröll, J.; Kohler, R.; Bruns, M.; Oberst, V.; Weidler, P. G.; Heißler, S.; Kübel, C.; Scherer, T.; Prang, R.; Seifert, H. J.; Pfleging, W.

    2013-03-01

    The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.

  7. Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

    NASA Technical Reports Server (NTRS)

    Fox, V. K.; Arvidson, R. E.; Jolliff, B. L.; Carpenter, P. K.; Catalano, J. G.; Hinkle, M. A. G.; Morris, R. V.

    2015-01-01

    Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

  8. Nano-sized manganese oxide: a proposed catalyst for water oxidation in the reaction of some manganese complexes and cerium(IV) ammonium nitrate.

    PubMed

    Najafpour, Mohammad Mahdi; Moghaddam, Atefeh Nemati

    2012-09-14

    According to UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy, nano-sized manganese oxides are proposed as active catalysts for water oxidation in the reaction of some manganese complexes and cerium(IV) ammonium nitrate. PMID:22806229

  9. Partial Alkane Oxidation Kinetics at High Pressures: Methane Oxidation in Stainless Steel and Quartz Reactors

    Microsoft Academic Search

    V. S. Arutyunov; V. M. Rudakov; V. I. Savchenko; E. V. Sheverdenkin; O. G. Sheverdenkina; A. Yu. Zheltyakov

    2002-01-01

    Homogeneous partial methane oxidation in quartz and stainless steel flow reactors was studied systematically in the pressure range 15–80 atm. Product yields were determined as functions of basic process parameters (pressure, temperature, residence time of the mixture in the reactor, initial oxygen concentration). The process was found to depend strongly on the material of the reactor surface.

  10. Alkane oxidation with manganese substituted polyoxometalates in aqueous media with ozone and the intermediacy of manganese ozonide species

    Microsoft Academic Search

    Ronny Neumann; Alexander M. Khenkin

    1998-01-01

    Manganese substituted polyoxometalates (POMs), such as Li12(MnII2ZnW(ZnW9O34)2) were effective catalysts for the oxidation of alkanes to ketones with ozone in an aqueous reaction medium; a green intermediate compound observ- able by UV-VIS and ESR at 278 °C was postulated to be a reactive manganese ozonide species. Transition metal substituted polyoxometalates have been stud- ied as oxidatively resistant analogues of metalloporphyrins.

  11. Distributions of Manganese, Iron, and Manganese-Oxidizing Bacteria In Lake Superior Sediments of Different Organic Carbon Content

    NASA Technical Reports Server (NTRS)

    Richardson, Laurie L.; Nealson, Kenneth H.

    1989-01-01

    Profiles of oxygen, soluble and particulate manganese and iron, organic carbon and nitrogen were examined in Lake Superior sediment cores, along with the distribution and abundance of heterotrophic and manganese oxidizing bacteria. Analyses were performed using cores collected with the submersible Johnson Sea Link II. Three cores, exhibiting a range of organic carbon content, were collected from the deepest basin in Lake Superior and the north and south ends of the Caribou trough, and brought to the surface for immediate analysis. Minielectrode profiles of oxygen concentration of the three cores were carried out using a commercially available minielectrode apparatus. Oxygen depletion to less than 1% occurred within 4 cm of the surface for two of the cores, but not until approximately 15 cm for the core from the south basin of the Caribou trough. The three cores exhibited very different profiles of soluble, as well as leachable, manganese and iron, suggesting different degrees of remobilization of these metals in the sediments. Vertical profiles of viable bacteria and Mn oxidizing bacteria, determined by plating and counting, showed that aerobic (and facultatively aerobic) heterotrophic bacteria were present at the highest concentrations near the surface and decreased steadily with depth, while Mn oxidizing bacteria were concentrations primarily at and above the oxic/anoxic interface. Soluble manganese in the pore waters, along with abundant organic carbon, appeared to enhance the presence of manganese oxidizing bacteria, even below the oxic/anoxic interface. Profiles of solid-phase leachable manganese suggested a microbial role in manganese reprecipitation in these sediments.

  12. Manganese oxide nanowires, films, and membranes and methods of making

    DOEpatents

    Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

    2008-10-21

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

  13. Polyaspartic acid coated manganese oxide nanoparticles for efficient liver MRI

    NASA Astrophysics Data System (ADS)

    Xing, Ruijun; Zhang, Fan; Xie, Jin; Aronova, Maria; Zhang, Guofeng; Guo, Ning; Huang, Xinglu; Sun, Xiaolian; Liu, Gang; Bryant, L. Henry; Bhirde, Ashwinkumar; Liang, Amy; Hou, Yanglong; Leapman, Richard D.; Sun, Shouheng; Chen, Xiaoyuan

    2011-12-01

    We report in this communication a simple, facile surface modification strategy to transfer hydrophobic manganese oxide nanoparticles (MONPs) into water by using polyaspartic acid (PASP). We systematically investigated the effect of the size of PASP-MONPs on MRI of normal liver and found that the particles with a core size of 10 nm exhibited greater enhancement than those with larger core sizes.We report in this communication a simple, facile surface modification strategy to transfer hydrophobic manganese oxide nanoparticles (MONPs) into water by using polyaspartic acid (PASP). We systematically investigated the effect of the size of PASP-MONPs on MRI of normal liver and found that the particles with a core size of 10 nm exhibited greater enhancement than those with larger core sizes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c1nr11242b

  14. Polyaspartic acid coated manganese oxide nanoparticles for efficient liver MRI.

    PubMed

    Xing, Ruijun; Zhang, Fan; Xie, Jin; Aronova, Maria; Zhang, Guofeng; Guo, Ning; Huang, Xinglu; Sun, Xiaolian; Liu, Gang; Bryant, L Henry; Bhirde, Ashwinkumar; Liang, Amy; Hou, Yanglong; Leapman, Richard D; Sun, Shouheng; Chen, Xiaoyuan

    2011-12-01

    We report in this communication a simple, facile surface modification strategy to transfer hydrophobic manganese oxide nanoparticles (MONPs) into water by using polyaspartic acid (PASP). We systematically investigated the effect of the size of PASP-MONPs on MRI of normal liver and found that the particles with a core size of 10 nm exhibited greater enhancement than those with larger core sizes. PMID:22064945

  15. Polyaspartic acid coated manganese oxide nanoparticles for efficient liver MRI†

    PubMed Central

    Xing, Ruijun; Zhang, Fan; Xie, Jin; Aronova, Maria; Zhang, Guofeng; Guo, Ning; Huang, Xinglu; Sun, Xiaolian; Liu, Gang; Bryant, L. Henry; Bhirde, Ashwinkumar; Liang, Amy; Hou, Yanglong; Leapman, Richard D.; Sun, Shouheng; Chen, Xiaoyuan

    2013-01-01

    We report in this communication a simple, facile surface modification strategy to transfer hydrophobic manganese oxide nanoparticles (MONPs) into water by using polyaspartic acid (PASP). We systematically investigated the effect of the size of PASP-MONPs on MRI of normal liver and found that the particles with a core size of 10 nm exhibited greater enhancement than those with larger core sizes. PMID:22064945

  16. Giant magnetoresistance of manganese oxides with a layered perovskite structure

    Microsoft Academic Search

    Y. Moritomo; A. Asamitsu; H. Kuwahara; Y. Tokura

    1996-01-01

    MANGANESE oxides with the cubic perovskite structure (typified by LaMnO3) have stimulated considerable interest because of their magnetoresistive properties1-9 they exhibit extremely large changes in electrical resistance in response to applied magnetic fields, a property that is of technological relevance for the development of magnetic memory and switching devices. But for such applications to be viable, great improvements will be

  17. A redox-assisted supramolecular assembly of manganese oxide nanotube

    SciTech Connect

    Tao Li [College of Chemistry and Chemical Engineering, Hunan University, Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China); Sun Chenggao [College of Chemistry and Chemical Engineering, Hunan University and Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China); Fan Meilian [College of Chemistry and Chemical Engineering, Hunan University, Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China); Huang Caijuan [College of Chemistry and Chemical Engineering, Hunan University, Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China); Wu Hailong [College of Chemistry and Chemical Engineering, Hunan University, Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China); Chao Zisheng [College of Chemistry and Chemical Engineering, Hunan University, Key Laboratory of Chemometrics and Chemical Biological Sensing Technologies, Ministry of Education, Changsha 410082 (China)]. E-mail: zschao@yahoo.com; Zhai Hesheng [College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)]. E-mail: hszhai@xmu.edu.cn

    2006-11-09

    In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO{sub 4} and MnCl{sub 2} as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N{sub 2} adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn{sup 3+} in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated.

  18. Laser microstructuring and annealing processes for lithium manganese oxide cathodes

    NASA Astrophysics Data System (ADS)

    Pröll, J.; Kohler, R.; Torge, M.; Ulrich, S.; Ziebert, C.; Bruns, M.; Seifert, H. J.; Pfleging, W.

    2011-09-01

    It is expected that cathodes for lithium-ion batteries (LIB) composed out of nano-composite materials lead to an increase in power density of the LIB due to large electrochemically active surface areas but cathodes made of lithium manganese oxides (Li-Mn-O) suffer from structural instabilities due to their sensitivity to the average manganese oxidation state. Therefore, thin films in the Li-Mn-O system were synthesized by non-reactive radiofrequency magnetron sputtering of a spinel lithium manganese oxide target. For the enhancement of the power density and cycle stability, large area direct laser patterning using UV-laser radiation with a wavelength of 248 nm was performed. Subsequent laser annealing processes were investigated in a second step in order to set up a spinel-like phase using 940 nm laser radiation at a temperature of 680 °C. The interaction processes between UV-laser radiation and the material was investigated using laser ablation inductively coupled plasma mass spectroscopy. The changes in phase, structure and grain shape of the thin films due to the annealing process were recorded using Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The structured cathodes were cycled using standard electrolyte and a metallic lithium anode. Different surface structures were investigated and a significant increase in cycling stability was found. Surface chemistry of an as-deposited as well as an electrochemically cycled thin film was investigated via X-ray photoelectron spectroscopy.

  19. STRUCTURE AND REACTIVITY STUDY OF BIOTIC AND ABIOTIC POORLY CRYSTALLINE MANGANESE OXIDES

    E-print Network

    Sparks, Donald L.

    STRUCTURE AND REACTIVITY STUDY OF BIOTIC AND ABIOTIC POORLY CRYSTALLINE MANGANESE OXIDES Rights Reserved #12;STRUCTURE AND REACTIVITY STUDY OF BIOTIC AND ABIOTIC POORLY CRYSTALLINE MANGANESE. Luther, III who inspired me on manganese reaction mechanisms in many helpful discussions, and Dr. Thomas

  20. Manganese ion-assisted assembly of superparamagnetic graphene oxide microbowls

    SciTech Connect

    Tian, Zhengshan [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing 210096 (China); School of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan 467000 (China); Xu, Chunxiang, E-mail: xcxseu@seu.edu.cn; Li, Jitao; Zhu, Gangyi; Xu, Xiaoyong; Dai, Jun; Shi, Zengliang; Lin, Yi [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing 210096 (China)

    2014-03-24

    A facile manganese ion Mn(II)-assisted assembly has been designed to fabricate microbowls by using graphene oxide nanosheets as basic building blocks, which were exfoliated ultrasonically from the oxidized soot powders in deionized water. From the morphology evolution observations of transmission electron microscope and scanning electron microscope, a coordinating-tiling-collapsing manner is proposed to interpret the assembly mechanism based on attractive Van der Waals forces, ?-? stacking, and capillary action. It is interesting to note that the as-prepared microbowls present a room temperature superparamagnetic behavior.

  1. Validation of In-Situ Iron-Manganese Oxide Coated Stream Pebbles as Sensors for Arsenic Source Monitoring

    NASA Astrophysics Data System (ADS)

    Blake, J.; Peters, S. C.; Casteel, A.

    2013-12-01

    Locating nonpoint source contaminant fluxes can be challenging due to the inherent heterogeneity of source and of the subsurface. Contaminants such as arsenic are a concern for drinking water quality and ecosystem health. Arsenic contamination can be the result of several natural and anthropogenic sources, and therefore it can be difficult to trace and identify major areas of arsenic in natural systems. Identifying a useful source indicator for arsenic is a crucial step for environmental remediation efforts. Previous studies have found iron-manganese oxide coated streambed pebbles as useful source indicators due to their high attraction for heavy metals in water. In this study, pebbles, surface water at baseflow and nearby rocks were sampled from the Pennypack Creek and its tributaries, in southwestern Pennsylvania, to test the ability of coated streambed pebbles as environmental source indicators for arsenic. Quartz pebbles, 5-7 cm in diameter, were sampled to minimize elemental contamination from rock chemistry. In addition, quartz provides an excellent substrate for iron and manganese coatings to form. These coatings were leached from pebbles using 4M nitric acid with 0.1% concentrated hydrochloric acid. Following sample processing, analyses were performed using an ICP-MS and the resulting data were spatially organized using ArcGIS software. Arsenic, iron and manganese concentrations in the leachate are normalized to pebble surface area and each location is reported as a ratio of arsenic to iron and manganese. Results suggest that iron-manganese coated stream pebbles are useful indicators of arsenic location within a watershed.

  2. Constraints on superoxide mediated formation of manganese oxides

    PubMed Central

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

    2013-01-01

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

  3. Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

    USGS Publications Warehouse

    Okita, P.M.; Maynard, J.B.; Spiker, E. C.; Force, E.R.

    1988-01-01

    Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

  4. Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural Requirements for Catalysis

    E-print Network

    Garfunkel, Eric

    systems based on water electrolysis to H2 and O2 is limited by availability of low- cost, earthPhotochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural different crystal structures, providing a rigorous test system to explore the significance of atomic

  5. Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using

    E-print Network

    Sparks, Donald L.

    Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using Quick Scanning X-ray Absorption parameters (3). The fate of chromium in soils has been extensively studied (4). Chromium is derived from both(VI) is mobile and more toxic than Cr(III), it is of great environmental concern. Chromium can be found naturally

  6. Manganese chlorins immobilized on silica as oxidation reaction catalysts.

    PubMed

    Castro, Kelly A D F; Pires, Sónia M G; Ribeiro, Marcos A; Simões, Mário M Q; Neves, M Graça P M S; Schreiner, Wido H; Wypych, Fernando; Cavaleiro, José A S; Nakagaki, Shirley

    2015-07-15

    Synthetic strategies that comply with the principles of green chemistry represent a challenge: they will enable chemists to conduct reactions that maximize the yield of products with commercial interest while minimizing by-products formation. The search for catalysts that promote the selective oxidation of organic compounds under mild and environmentally friendly conditions constitutes one of the most important quests of organic chemistry. In this context, metalloporphyrins and analogues are excellent catalysts for oxidative transformations under mild conditions. In fact, their reduced derivatives chlorins are also able to catalyze organic compounds oxidation effectively, although they have been still little explored. In this study, we synthesized two chlorins through porphyrin cycloaddition reactions with 1.3-dipoles and prepared the corresponding manganese chlorins (MnCHL) using adequate manganese(II) salts. These MnCHL were posteriorly immobilized on silica by following the sol-gel process and the resulting solids were characterized by powder X-ray diffraction (PXRD), UVVIS spectroscopy, FTIR, XPS, and EDS. The catalytic activity of the immobilized MnCHL was investigated in the oxidation of cyclooctene, cyclohexene and cyclohexane and the results were compared with the ones obtained under homogeneous conditions. PMID:25841060

  7. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Kang, J.-K.; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ??REEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ??REE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect the redox conditions of seawater. The concentration of elements in hydrogenetic Fe-Mn crusts depends on a wide variety of water column and crust surface characteristics, whereas concentration of elements in hydrothermal oxide deposits depends of the intensity of leaching, rock types leached, and precipitation of sulphides at depth in the hydrothermal system.

  8. Thursday, November 8, 2007 -9:15 AM Effects of Environmental Conditions on the Properties of Biogenic Manganese Oxides.

    E-print Network

    Sparks, Donald L.

    of Biogenic Manganese Oxides. Mengqiang Zhu, Sanjai Parikh, Matt Ginder-Vogel, and Donald L. Sparks. Plant in the critical zone, have been found to mediate aqueous Mn(II) oxidation to form biogenic manganese oxides (BioMnOx). Microbially mediated BioMnOx are thought to be one of the major sources of manganese oxides in soils. Recent

  9. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

    Johnson, Christopher S. (Naperville, IL); Kang, Sun-Ho (Naperville, IL); Thackeray, Michael M. (Naperville, IL)

    2009-12-22

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0.5

  10. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M. (Naperville, IL); Johnson, Christopher S. (Naperville, IL); Li, Naichao (Croton on Hudson, NY)

    2007-12-04

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0

  11. Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

    2012-04-28

    CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (? > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. PMID:22382465

  12. Preparation and characterization of manganese oxide\\/CNT composites as supercapacitive materials

    Microsoft Academic Search

    Zhen Fan; Jinhua Chen; Mingyong Wang; Kunzai Cui; Haihui Zhou; Yafei Kuang

    2006-01-01

    Manganese oxide was synthesized and dispersed on carbon nanotube (CNT) matrix by thermally decomposing manganese nitrates. CNTs used in this paper were grown directly on graphite disk by chemical vapor deposition technique. The capacitive behavior of manganese oxide\\/CNT composites was investigated by cyclic voltammetry and galvanostatic charge–discharge method in 1 M Na2SO4 aqueous solutions. When the loading mass of MnO2

  13. Solution synthesis and characterization of lithium manganese oxide cathode materials

    SciTech Connect

    Voigt, J.A.; Boyle, T.J.; Doughty, D.H. [and others

    1995-07-01

    A nonaqueous coprecipitation process has been developed to prepare controlled stoichiometry lithium manganese oxalate precipitates. The process involved mixing a methanolic Li-Mn nitrate solution with a methanolic solution containing tetramethylammonium oxalate as the precipitating agent. The resulting oxalates were readily converted to a variety of phase pure lithium manganese oxides at moderate temperatures ({le}600{degrees}C), where the phase formed was determined by the initial Li/Mn ratio in the starting solution. Metal cation dopants have been incorporated into the oxalate precipitate by dissolving the appropriate metal nitrate in the Li-Mn precursor solution The various starting solutions, oxalate precipitates, and calcined oxides have been extensively characterized using a variety of techniques, including {sup 7}Li NMR, TGA/DTA, SEM, and XRD. Results indicate that a strong interaction occurs between Li and Mn in the nitrate solution which carries over into the oxalate phase during precipitation. The morphology and the crystallite size of the oxide powders were shown to be controlled by the morphology of the oxalate precursor and the oxalate calcination temperature, respectively. The results of initial cathode performance tests with respect to dopant type (Al, Ni, Co) and concentration for LiMn{sub 2}O{sub 4} are also reported.

  14. New Vanadium and Manganese Oxides for Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Whittingham, M. Stanley; Zavalij, Peter Y.; Chirayil, Thomas; Chen, Rongji

    1997-03-01

    Transition metal oxides, that can intercalate lithium ions in a reversible manner and with an energy in the range of 3 to 4 volts, are a critical link in the advancement of high energy density lithium batteries. Vanadium, manganese and iron oxides form the appropriate polyhedral structures that might intercalate small ions. Such structures have been formed at low temperatures under conditions of kinetic rather than thermodynamic control. In the case of vanadium six new compounds have been formed using the tetramethylammonium ion, TMA, as the structure directing agent. One of these is a new form of vanadium dioxide, a perfect form of the vanadium pentoxide structure, which is electrochemically active and can intercalate a wide range of molecular and ionic species. Others contain the TMA cation and have layered lattices. A new magnetically active form of nickel manganate has also been synthesized, as have several layered alkali metal manganese oxides with the titanium disulfide type lattice. Their structural characterization and property determination will be described. Supported by NSF-DMR.

  15. Manganese-doped zinc oxide tetratubes and their photoluminescent properties

    NASA Astrophysics Data System (ADS)

    Xu, C. X.; Sun, X. W.; Dong, Z. L.; Tan, S. T.; Cui, Y. P.; Wang, B. P.

    2005-12-01

    Based on vapor-phase transport method, manganese-doped zinc oxide (ZnO:Mn) tetropod whiskers were fabricated. The pods of the ZnO:Mn whiskers show hexagonal hollow shape with multitips at the front. X-ray diffraction and high-resolution transmission electron microscopy demonstrate that the tube pods and the tips are composed of wurtzite ZnO growing along [0001] direction. The generation of the luminescent center in ZnO whiskers and electron transport between the ground state and the excitation states of Mn2+ are analyzed by Raman-scattering, photoluminescence, and photoluminescent excitation measurements.

  16. Nanostructured manganese oxides and their composites with carbon nanotubes as electrode materials for energy storage devices

    Microsoft Academic Search

    V. Subramanian; Hongwei Zhu; Bingqing Wei

    2008-01-01

    Manganese oxides have been synthesized by a variety of techniques in different nanostructures and studied for their properties as electrode materials in two different storage applications, supercapacitors (SCs) and Li-ion batteries. The composites involving carbon nanotubes (CNTs) and manganese oxides were also prepared by a simple room-temperature method and evaluated as electrode materials in the above applications. The synthesis of

  17. Population Structure of Manganese-Oxidizing Bacteria in Stratified Soils and Properties of Manganese Oxide Aggregates under Manganese–Complex Medium Enrichment

    PubMed Central

    Zhang, Zhongming; Chen, Hong; Liu, Jin; Ali, Muhammad; Liu, Fan; Li, Lin

    2013-01-01

    Manganese-oxidizing bacteria in the aquatic environment have been comprehensively investigated. However, little information is available about the distribution and biogeochemical significance of these bacteria in terrestrial soil environments. In this study, stratified soils were initially examined to investigate the community structure and diversity of manganese-oxidizing bacteria. Total 344 culturable bacterial isolates from all substrata exhibited Mn(II)-oxidizing activities at the range of 1 µM to 240 µM of the equivalent MnO2. The high Mn(II)-oxidizing isolates (>50 mM MnO2) were identified as the species of phyla Actinobacteria, Firmicutes and Proteobacteria. Seven novel Mn(II)-oxidizing bacterial genera (species), namely, Escherichia, Agromyces, Cellulomonas, Cupriavidus, Microbacterium, Ralstonia, and Variovorax, were revealed via comparative phylogenetic analysis. Moreover, an increase in the diversity of soil bacterial community was observed after the combined enrichment of Mn(II) and carbon-rich complex. The phylogenetic classification of the enriched bacteria represented by predominant denaturing gradient gel electrophoresis bands, was apparently similar to culturable Mn(II)-oxidizing bacteria. The experiments were further undertaken to investigate the properties of the Mn oxide aggregates formed by the bacterial isolates with high Mn(II)-oxidizing activity. Results showed that these bacteria were closely encrusted with their Mn oxides and formed regular microspherical aggregates under prolonged Mn(II) and carbon-rich medium enrichment for three weeks. The biotic oxidation of Mn(II) to Mn(III/IV) by these isolates was confirmed by kinetic examinations. X-ray diffraction assays showed the characteristic peaks of several Mn oxides and rhodochrosite from these aggregates. Leucoberbelin blue tests also verified the Mn(II)-oxidizing activity of these aggregates. These results demonstrated that Mn oxides were formed at certain amounts under the enrichment conditions, along with the formation of rhodochrosite in such aggregates. Therefore, this study provides insights into the structure and diversity of soil-borne bacterial communities in Mn(II)-oxidizing habitats and supports the contribution of soil-borne Mn(II)-oxidizing bacteria to Mn oxide mineralization in soils. PMID:24069232

  18. Catalytic asymmetric oxidations using optically active (salen)manganese(III) complexes as catalysts

    Microsoft Academic Search

    Tsutomu Katsuki

    1995-01-01

    This review deals with enantioselective one oxygen atom transfer reactions (epoxidation, oxidation of enolates, and oxidation of sulphide to sulphoxides) catlaysed by optically active (salen)manganese(III)complexes. Asymmetric aziridination is also discussed briefly.

  19. Monday, November 5, 2007 -9:30 AM Real-Time Surface-Chemistry of Arsenite Oxidation by Hydrous Manganese Oxide.

    E-print Network

    Sparks, Donald L.

    by Hydrous Manganese Oxide. Matthew Ginder-Vogel and Donald L. Sparks. University of Delaware, 152 Townsend(V)) by manganese(IV) oxide is an important reaction impacting the natural cycling of As. The aresenite species(III) on the surface of manganese oxides has been well characterized; however, the surface chemistry of the oxidation

  20. Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

    PubMed Central

    2011-01-01

    Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts. PMID:21639896

  1. Interaction of inorganic arsenic with biogenic manganese oxide produced by a Mn-oxidizing fungus, strain KR21-2.

    PubMed

    Tani, Yukinori; Miyata, Naoyuki; Ohashi, Maiko; Ohnuki, Toshihiko; Seyama, Haruhiko; Iwahori, Keisuke; Soma, Mitsuyuki

    2004-12-15

    In batch culture experiments we examined oxidation of As(III) and adsorption of As(III/V) by biogenic manganese oxide formed by a manganese oxide-depositing fungus, strain KR21-2. We expected to gain insight into the applicability of Mn-depositing microorganisms for biological treatment of As-contaminated waters. In cultures containing Mn2+ and As(V), the solid Mn phase was rich in bound Mn2+ (molar ratio, approximately 30%) and showed a transiently high accumulation of As(V) during the early stage of manganese oxide formation. As manganese oxide formation progressed, a large proportion of adsorbed As(V) was subsequently released. The high proportion of bound Mn2+ may suppress a charge repulsion between As(V) and the manganese oxide surface, which has structural negative charges, promoting complex formation. In cultures containing Mn2+ and As(III), As(III) started to be oxidized to As(V) after manganese oxide formation was mostly completed. In suspensions of the biogenic manganese oxides with dissolved Mn2+, As(III) oxidation rates decreased with increasing dissolved Mn2+. These results indicate that biogenic manganese oxide with a high proportion of bound Mn2+ oxidizes As(III) less effectively than with a low proportion of bound Mn2+. Coexisting Zn2+, Ni2+, and Co2+ also showed similar effects to different extents. The present study demonstrates characteristic features of oxidation and adsorption of As by biogenic manganese oxides and suggests possibilities of developing a microbial treatment system for water contaminated with As that is suited to the actual situation of contamination. PMID:15669320

  2. KINETICS AND MECHANISMS OF CHROMIUM(III) OXIDATION AND PRECIPITATION ON MANGANESE OXIDES, IN REAL-TIME AND AT THE

    E-print Network

    Sparks, Donald L.

    KINETICS AND MECHANISMS OF CHROMIUM(III) OXIDATION AND PRECIPITATION ON MANGANESE OXIDES, IN REAL Summer 2010 Copyright 2010 Gautier Landrot All Rights Reserved #12;KINETICS AND MECHANISMS OF CHROMIUM

  3. A soluble form of nano-sized colloidal manganese(IV) oxide as an efficient catalyst for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi

    2011-04-21

    A soluble form of colloidal manganese(IV) oxide showed efficient oxygen evolution or water oxidation in presence of oxone, H(2)O(2), cerium(IV) ammonium nitrate and tris(2,2'-bipyridyl)ruthenium(III). PMID:21359392

  4. Manganese

    MedlinePLUS

    ... iron, zincTaking calcium along with any of these minerals can decrease the amount of manganese that the body can take in.IP-6 (Phytic acid)IP-6 found in foods, such as cereals, nuts, and beans, and in supplements can decrease the amount of ...

  5. Porous manganese oxide octahedral molecular sieves and octahedral layered materials.

    PubMed

    Suib, Steven L

    2008-04-01

    This Account first gives a historical overview of the development of octahedral molecular sieve (OMS) and octahedral layer (OL) materials based on porous mixed-valent manganese oxides. Unique properties of such systems include excellent semiconductivity and porosity. Materials that are conducting and porous are rare and can offer novel properties not normally available with most molecular sieve materials. The good semiconductivity of OMS and OL systems not only permits potential applications of the conductivity of these materials but also allows characterization of these systems where charging effects are often a problem. Porous manganese oxide natural materials are found as manganese nodules, and these materials when dredged from the ocean floors have been used as excellent adsorbents of metals such as from electroplating wastes and have been shown to be excellent catalysts. Rational for synthesis of novel OMS and OL materials is related to the superb conductivity, microporosity, and catalytic activity of these natural materials. The natural systems are often found as mixtures, are poorly crystalline, and have incredibly diverse compositions due to exposure to various aqueous environments in nature. Such exposure allows ion exchange to occur. Preparation of pure crystalline OL and OMS systems is one of the very significant goals of this work. The status of this research area is one of moderate development. Opportunities exist for preparation of a multitude of novel materials. Some applications of these materials have recently been achieved primarily in the area of catalysis and membranes, and others such as sensors and adsorptive systems are likely. Characterization studies are becoming more sophisticated as new materials and proper preparation of materials for such characterization studies are being done. The research area involved in this work is solid state chemistry. The fields of materials synthesis, characterization, and applications of materials are all important in developments of this field. Researchers in chemistry, chemical engineering, materials science, physics, and biological sciences are actively pursuing research in this area. The most significant results found in this work are related to the novel structural and physical properties of porous manganese oxide materials. Variable pore size materials have been synthesized using structure directors and with a variety of synthetic methodologies. Transformations of tunnel materials with temperature and in specific atmosphere have recently been studied with in situ synchrotron methods. Conductivities of these materials appear to be related to the structural properties of these systems with more open structures being less conductive. Catalytic properties of these OMS and OL materials have been shown to be related to the redox cycling of various oxidations states of manganese such as Mn2+, Mn3+, and Mn4+. Chemists interested in synthesis of new materials, the chemistry of solids, enhancing the rates of catalytic reactions, and finding new applications of materials would be interested in these novel materials. Fundamental properties of electron transfer are critical to this research. Concepts of nonstoichiometry, defects, oxygen vacancies, and intermediates are fundamental to many of the syntheses, characterization, and applications such as fuel cells, catalysis, adsorption, sensors, batteries, and related applications. PMID:18232663

  6. Sol-gel synthesis and adsorption properties of mesoporous manganese oxide

    NASA Astrophysics Data System (ADS)

    Ivanets, A. I.; Kuznetsova, T. F.; Prozorovich, V. G.

    2015-03-01

    Sol-gel synthesis of mesoporous xerogels of manganese oxide with different phase compositions has been performed. The manganese oxide sols were obtained by redox reactions of potassium permanganate with hydrogen peroxide or manganese(II) chloride in aqueous solutions. The isotherms of the low-temperature adsorption-desorption of nitrogen with manganese oxide xerogels treated at 80, 200, 400, and 600°C were measured. The samples were studied by electron microscopy and thermal and XRD analysis. The phase transformation and the changes in the adsorption and capillary-condensation properties of manganese oxide were shown to depend on the sol synthesis conditions and the temperature of the thermal treatment of the gel. The X-ray amorphous samples heated at 80°C were shown to have low values of the specific surface; at higher temperatures, the xerogel crystallized into mixed phases with various compositions and its surface area increased at 200-400°C and decreased at 600°C.

  7. Manganese oxide minerals: Crystal structures and economic and environmental significance

    PubMed Central

    Post, Jeffrey E.

    1999-01-01

    Manganese oxide minerals have been used for thousands of years—by the ancients for pigments and to clarify glass, and today as ores of Mn metal, catalysts, and battery material. More than 30 Mn oxide minerals occur in a wide variety of geological settings. They are major components of Mn nodules that pave huge areas of the ocean floor and bottoms of many fresh-water lakes. Mn oxide minerals are ubiquitous in soils and sediments and participate in a variety of chemical reactions that affect groundwater and bulk soil composition. Their typical occurrence as fine-grained mixtures makes it difficult to study their atomic structures and crystal chemistries. In recent years, however, investigations using transmission electron microscopy and powder x-ray and neutron diffraction methods have provided important new insights into the structures and properties of these materials. The crystal structures for todorokite and birnessite, two of the more common Mn oxide minerals in terrestrial deposits and ocean nodules, were determined by using powder x-ray diffraction data and the Rietveld refinement method. Because of the large tunnels in todorokite and related structures there is considerable interest in the use of these materials and synthetic analogues as catalysts and cation exchange agents. Birnessite-group minerals have layer structures and readily undergo oxidation reduction and cation-exchange reactions and play a major role in controlling groundwater chemistry. PMID:10097056

  8. Cyanamide route to calcium-manganese oxide foams for water oxidation.

    PubMed

    Baktash, Elham; Zaharieva, Ivelina; Schröder, Marc; Goebel, Caren; Dau, Holger; Thomas, Arne

    2013-12-28

    In nature, photosynthetic water oxidation is efficiently catalysed at a protein-bound ?-oxido Mn4Ca cluster. This cluster consists of earth abundant, non-toxic elements and serves as a paragon for development of synthetic catalysts. In this study we developed porous calcium-manganese oxides with a unique foam-like nanostructure prepared via a facile and robust synthetic route using cyanamide as a porogen. A series of such oxide foams annealed at different temperatures was characterized by TEM, SEM, XRD, N2 physisorption, and X-ray absorption spectroscopy (XAS) in order to correlate crystallinity, atomic structure, surface area and oxidation state of the materials with catalytic activity. Some of the resulting Ca-Mn oxides show high activity as catalysts for water oxidation in the presence of cerium(iv) ammonium nitrate as a non-oxo transfer oxidant. An amorphous calcium-manganese-oxide foam with 130 m(2) g(-1) surface area and Mn oxidation state of +3.6 was identified to be most active; its activity is superior to previously reported Ca-Mn oxides. At the atomic level, this material shares structural motifs with the biological paragon as revealed by dual-edge XAS at the Mn and Ca K-edge. Rather than nanostructure and surface area, the atomic structure of the Ca-Mn oxide and the extent of structural order appear to be crucial determinants of catalytic activity. Fully disordered low-valent Mn materials as well as high-valent but crystalline Mn-Ca oxides are unreactive. Highly disordered variants of layered manganese oxide with Ca and water molecules interfacing layer fragments are most reactive. PMID:24091767

  9. Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction

    SciTech Connect

    Lee, Ji-Hoon; Kennedy, David W.; Dohnalkova, Alice; Moore, Dean A.; Nachimuthu, Ponnusamy; Reed, Samantha B.; Fredrickson, Jim K.

    2011-12-13

    The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced {gamma}-MnS (rambergite) nanoparticles during the concurrent reduction of MnO{sub 2} and thiosulfate coupled to H{sub 2} oxidation. To investigate effect of direct microbial reduction of MnO{sub 2} on MnS formation, two MR-1 mutants defective in outer membrane c-type cytochromes ({Delta}mtrC/{Delta}omcA and {Delta}mtrC/{Delta}omcA/{Delta}mtrF) were also used and it was determined that direct reduction of MnO{sub 2} was dominant relative to chemical reduction by biogenic sulfide generated from thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of strain MR-1 with lactate as the electron donor produced MnCO{sub 3} (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO{sub 3} formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions expected to favor the precipitation of MnS. Formation of MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modeling predictions. Biogenic manganese sulfide may be a manganese sink in the Mn biogeochemical cycle in select environments such as deep anoxic marine basins within the Baltic Sea.

  10. Uncovering structure-activity relationships in manganese-oxide-based heterogeneous catalysts for efficient water oxidation.

    PubMed

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

    2015-03-01

    Artificial photosynthesis by harvesting solar light into chemical energy could solve the problems of energy conversion and storage in a sustainable way. In nature, CO2 and H2 O are transformed into carbohydrates by photosynthesis to store the solar energy in chemical bonds and water is oxidized to O2 in the oxygen-evolving center (OEC) of photosystem II (PS II). The OEC contains CaMn4 O5 cluster in which the metals are interconnected through oxido bridges. Inspired by biological systems, manganese-oxide-based catalysts have been synthesized and explored for water oxidation. Structural, functional modeling, and design of the materials have prevailed over the years to achieve an effective and stable catalyst system for water oxidation. Structural flexibility with eg (1) configuration of Mn(III) , mixed valency in manganese, and higher surface area are the main requirements to attain higher efficiency. This Minireview discusses the most recent progress in heterogeneous manganese-oxide-based catalysts for efficient chemical, photochemical, and electrochemical water oxidation as well as the structural requirements for the catalyst to perform actively. PMID:25641823

  11. Vanadia supported on nickel manganese oxide nanocatalysts for the catalytic oxidation of aromatic alcohols

    NASA Astrophysics Data System (ADS)

    Adil, Syed F.; Alabbad, Saad; Kuniyil, Mufsir; Khan, Mujeeb; Alwarthan, Abdulrahman; Mohri, Nils; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq Hussain

    2015-02-01

    Vanadia nanoparticles supported on nickel manganese mixed oxides were synthesized by co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as oxidant. It was observed that the calcination temperature and the size of particles play an important role in the catalytic process. The catalyst was evaluated for its oxidation property against aliphatic and aromatic alcohols, which was found to display selectivity towards aromatic alcohols. The samples were characterized by employing scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, thermogravimetric analysis, and X-ray photoelectron spectroscopy.

  12. Vanadia supported on nickel manganese oxide nanocatalysts for the catalytic oxidation of aromatic alcohols.

    PubMed

    Adil, Syed F; Alabbad, Saad; Kuniyil, Mufsir; Khan, Mujeeb; Alwarthan, Abdulrahman; Mohri, Nils; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq Hussain

    2015-01-01

    Vanadia nanoparticles supported on nickel manganese mixed oxides were synthesized by co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as oxidant. It was observed that the calcination temperature and the size of particles play an important role in the catalytic process. The catalyst was evaluated for its oxidation property against aliphatic and aromatic alcohols, which was found to display selectivity towards aromatic alcohols. The samples were characterized by employing scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, thermogravimetric analysis, and X-ray photoelectron spectroscopy. PMID:25852349

  13. Manganese oxide microswitch for electronic memory based on neural networks

    NASA Technical Reports Server (NTRS)

    Ramesham, R.; Daud, T.; Moopenn, A.; Thakoor, A. P.; Khanna, S. K.

    1989-01-01

    A solid-state, resistance tailorable, programmable-once, binary, nonvolatile memory switch based on manganese oxide thin films is reported. MnO(x) exhibits irreversible memory switching from conducting (on) to insulating (off) state, with the off and on resistance ratio of greater than 10,000. The switching mechanism is current-triggered chemical transformation of a conductive MnO(2-Delta) to an insulating Mn2O3 state. The energy required for switching is of the order of 4-20 nJ/sq micron. The low switching energy, stability of the on and off states, and tailorability of the on state resistance make these microswitches well suited as programmable binary synapses in electronic associative memories based on neural network models.

  14. Sol-gel synthesis and characterization of mesoporous manganese oxide

    SciTech Connect

    Hong Xinlin; Zhang Gaoyong; Zhu Yinyan; Yang Hengquan

    2003-10-30

    Mesoporous manganese oxide (MPMO) from reduction of KMnO{sub 4} with maleic acid, was obtained and characterized in detail. The characterization of the material was confirmed by high-resolution transmission electron microscopy (HRTEM), X-ray powder diffractometry (XRD) and N{sub 2} sorptometry. The results showed that MPMO is a pseudo-crystalline material with complex network pore structure, of which BET specific surface area is 297 m{sup 2}/g and pore size distribution is approximately in the range of 0.7-6.0 nm. The MPMO material turns to cryptomelane when the calcinating temperature rises to 400 deg. C. The optimum sol-gel reaction conditions are KMnO{sub 4}/C{sub 4}H{sub 4}O{sub 4} molar ratio=3, pH=7 and gelation time>6 h.

  15. Resistive switching properties of manganese oxide nanoparticles with hexagonal shape

    NASA Astrophysics Data System (ADS)

    Hu, Quanli; Park, Mira; Abbas, Yawar; Kim, Jai Soon; Yoon, Tae-Sik; Choi, Young Jin; Kang, Chi Jung

    2015-01-01

    Uniformly sized hexagonal shaped manganese oxide (MnO) nanoparticles were chemically synthesized. The bipolar resistive switching characteristics were investigated in the Ti/MnO/Pt structure. The nanoparticles were assembled as close-packed monolayer with a thickness of 30 nm by dip-coating and annealing procedures. The bipolar resistive switching behaviors in Ti/MnO/Pt device could be caused by the formation and rupture of conductive filaments in the nanoparticles. The temperature dependence of resistance was discussed. The resistance of HRS presented a negative temperature dependence at high temperature, indicating a typical semiconducting behavior. The resistance of LRS increased with the elevated temperature exhibiting a metallic state. Ohmic conduction, space charge limited conduction (SCLC), and Schottky conduction have been investigated for the conduction and switching mechanism.

  16. Manganese Peroxidase Degrades Pristine but Not Surface-Oxidized (Carboxylated) Single-Walled Carbon Nanotubes

    E-print Network

    Alvarez, Pedro J.

    Manganese Peroxidase Degrades Pristine but Not Surface-Oxidized (Carboxylated) Single-Walled Carbon ligninolytic enzymes: lignin perox- idase, manganese peroxidase (MnP), and laccase. Only MnP was capable peroxidase (HRP) in the presence of 40 M H2O2 and proposed that the reactive oxygen species (ROS) generated

  17. The Wettability of a Multi-Component DNAPL on Quartz and Iron Oxide Sands

    NASA Astrophysics Data System (ADS)

    Molnar, I.; O'Carroll, D.; Gerhard, J.

    2009-05-01

    Dense nonaqueous phase liquids (DNAPLs) released to the subsurface often contain a variety of chemical constituents, via either co-disposal or intentional modification to increase their industrial efficacy. These additional constituents are often surface active compounds (surfactants)that partition to soil surfaces. The role that these surface active compounds that sorb to soil surfaces have on DNAPL migration is still poorly understood despite an increasing amount of work in the area. Most studies have focused on the role surface active chemicals play in altering the wettability of quartz sands. This research aims to extend the understanding of multi-component DNAPL transport to other porous media and under a variety of pH conditions. Specifically, the objective of this study was to compare the changes in the wettability of quartz and iron oxide sands in a tetrachloroethylene (PCE)/water system spiked with dodecylamine, a representative cationic surfactant. Wettability was assessed through: (i) contact angles measured on representative quartz and iron oxide-coated plates as well as (ii) contact angles measured directly on sands using an Axial Drop Symmetrical Analyzer apparatus; and (iii) capillary pressure-saturation relationships obtained via multi-step outflow experiments. In addition, two-dimensional sandbox experiments explored the influences of iron oxide and quartz sands on multicomponent DNAPL migration. Results suggest that quartz and iron oxide-coated sands exhibit different wetting characteristics under similar subsurface conditions.

  18. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

    PubMed Central

    Birkner, Nancy; Navrotsky, Alexandra

    2014-01-01

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

  19. Sodium perxenate permits rapid oxidation of manganese for easy spectrophotometric determination

    NASA Technical Reports Server (NTRS)

    Bane, R. W.

    1967-01-01

    Sodium perxenate oxidizes manganese to permanganate almost instantaneously in dilute acid solution and without a catalyst. A solution is prepared by dissolving 200 mg of sodium perxenate in distilled water and diluting to 100 ml.

  20. Adhesion enhancement of indium tin oxide (ITO) coated quartz optical fibers

    NASA Astrophysics Data System (ADS)

    Wang, Yihua; Liu, Jing; Wu, Xu; Yang, Bin

    2014-07-01

    Transparent conductive indium tin oxide (ITO) film was prepared on optical fiber through a multi-step sol-gel process. The influence of annealing temperature on the adhesion of ITO coated optical fibers was studied. Different surface treatments were applied to improve the adhesion between ITO film and quartz optical fiber. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction analysis (XRD), UV-vis spectrophotometer and Avometer were used to characterize the morphology, crystal structure and photo-electric properties. A thermal shock test was used to evaluate the adhesion. The result shows that the adhesion between ITO film and quartz optical fiber can be strongly influenced by the annealing process, and optimal adhesion can be acquired when annealing temperature is 500 °C. Surface treatments of ultrasonic cleaning and the application of surface-active agent have effectively enhanced the adhesion and photo-electric properties of indium tin oxide film coated quartz optical fiber.

  1. Manganese Oxide Film Electrodes Prepared by Electrostatic Spray Deposition for Electrochemical Capacitors

    Microsoft Academic Search

    Kyung-Wan Nam; Kwang-Bum Kim

    2006-01-01

    Porous manganese oxide thin film electrodes were prepared for use in electrochemical capacitors by electrostatic spray deposition. The as-prepared manganese oxide film showed ideal capacitive behavior after potential cycling within the range of 0.1 to 0.9 V vs saturated calomel electrode in a0 .1 MN a2SO4 electrolyte. Analysis of the X-ray diffraction, X-ray absorption spectroscopy, and Raman scattering data during

  2. Fischer-Tropsch kinetic studies with cobalt-manganese oxide catalysts

    Microsoft Academic Search

    Martin J. Keyser; Raymond C. Everson; Rafael L. Espinoza

    2000-01-01

    An investigation was undertaken to establish the reaction mechanism for the Fischer-Tropsch reaction, in the presence of the water-gas shift reaction, over a cobalt-manganese oxide catalyst under conditions favoring the formation of gaseous, liquid, and solid (waxes) hydrocarbons (210--250 C and 6--26 bar). A micro-fixed-bed reactor was used with a cobalt-manganese oxide catalyst prepared by a coprecipitation method. An integral

  3. Prophylactic use of polyvinylpyridine-N-oxide (PVNO) in baboons exposed to quartz dust

    SciTech Connect

    Goldstein, B.; Rendall, R.E.G.

    1987-04-01

    Twelve baboons were exposed to a quartz dust cloud. Four of these were also given polyvinylpyridine-N-oxide (PVNO) by aerosol and four received PVNO by aerosol and injection. A prophylactic effect was demonstrated during the course of treatment, but when treatment stopped the silicosis progressed to the same degree of severity as in the untreated animals.

  4. Hawaiian submarine manganese-iron oxide crusts - A dating tool?

    USGS Publications Warehouse

    Moore, J.G.; Clague, D.A.

    2004-01-01

    Black manganese-iron oxide crusts form on most exposed rock on the ocean floor. Such crusts are well developed on the steep lava slopes of the Hawaiian Ridge and have been sampled during dredging and submersible dives. The crusts also occur on fragments detached from bedrock by mass wasting, on submerged coral reefs, and on poorly lithified sedimentary rocks. The thickness of the crusts was measured on samples collected since 1965 on the Hawaiian Ridge from 140 dive or dredge localities. Fifty-nine (42%) of the sites were collected in 2001 by remotely operated vehicles (ROVs). The thinner crusts on many samples apparently result from post-depositional breakage, landsliding, and intermittent burial of outcrops by sediment. The maximum crust thickness was selected from each dredge or dive site to best represent crusts on the original rock surface at that site. The measurements show an irregular progressive thickening of the crusts toward the northwest-i.e., progressive thickening toward the older volcanic features with increasing distance from the Hawaiian hotspot. Comparison of the maximum crust thickness with radiometric ages of related subaerial features supports previous studies that indicate a crust-growth rate of about 2.5 mm/m.y. The thickness information not only allows a comparison of the relative exposure ages of two or more features offshore from different volcanoes, but also provides specific age estimates of volcanic and landslide deposits. The data indicate that some of the landslide blocks within the south Kona landslide are the oldest exposed rock on Mauna Loa, Kilauea, or Loihi volcanoes. Crusts on the floors of submarine canyons off Kohala and East Molokai volcanoes indicate that these canyons are no longer serving as channelways for downslope, sediment-laden currents. Mahukona volcano was approximately synchronous with Hilo Ridge, both being younger than Hana Ridge. The Nuuanu landslide is considerably older than the Wailau landslide. The Waianae landslide southwest of Oahu has yielded samples with the greatest manganese-iron oxide crusts (9.5 mm thick) and therefore apparently represents the oldest submarine material yet found in the study area. The submarine volcanic field 100 km southwest of Oahu is apparently younger than the Waianae landslide. ?? 2004 Geological Society of America.

  5. Extracellular zinc competitively inhibits manganese uptake and compromises oxidative stress management in Streptococcus pneumoniae.

    PubMed

    Eijkelkamp, Bart A; Morey, Jacqueline R; Ween, Miranda P; Ong, Cheryl-lynn Y; McEwan, Alastair G; Paton, James C; McDevitt, Christopher A

    2014-01-01

    Streptococcus pneumoniae requires manganese for colonization of the human host, but the underlying molecular basis for this requirement has not been elucidated. Recently, it was shown that zinc could compromise manganese uptake and that zinc levels increased during infection by S. pneumoniae in all the niches that it colonized. Here we show, by quantitative means, that extracellular zinc acts in a dose dependent manner to competitively inhibit manganese uptake by S. pneumoniae, with an EC50 of 30.2 µM for zinc in cation-defined media. By exploiting the ability to directly manipulate S. pneumoniae accumulation of manganese, we analyzed the connection between manganese and superoxide dismutase (SodA), a primary source of protection for S. pneumoniae against oxidative stress. We show that manganese starvation led to a decrease in sodA transcription indicating that expression of sodA was regulated through an unknown manganese responsive pathway. Intriguingly, examination of recombinant SodA revealed that the enzyme was potentially a cambialistic superoxide dismutase with an iron/manganese cofactor. SodA was also shown to provide the majority of protection against oxidative stress as a S. pneumoniae ?sodA mutant strain was found to be hypersensitive to oxidative stress, despite having wild-type manganese levels, indicating that the metal ion alone was not sufficiently protective. Collectively, these results provide a quantitative assessment of the competitive effect of zinc upon manganese uptake and provide a molecular basis for how extracellular zinc exerts a 'toxic' effect on bacterial pathogens, such as S. pneumoniae. PMID:24558498

  6. Oxidative damage and neurodegeneration in manganese-induced neurotoxicity

    SciTech Connect

    Milatovic, Dejan [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States)], E-mail: dejan.milatovic@vanderbilt.edu; Zaja-Milatovic, Snjezana [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Gupta, Ramesh C. [Murray State University, Breathitt Veterinary Center, Hopkinsville, KY (United States); Yu, Yingchun [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Aschner, Michael [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Pharmacology and the Kennedy Center for Research on Human Development, Nashville, TN (United States)

    2009-10-15

    Exposure to excessive manganese (Mn) levels results in neurotoxicity to the extrapyramidal system and the development of Parkinson's disease (PD)-like movement disorder, referred to as manganism. Although the mechanisms by which Mn induces neuronal damage are not well defined, its neurotoxicity appears to be regulated by a number of factors, including oxidative injury, mitochondrial dysfunction and neuroinflammation. To investigate the mechanisms underlying Mn neurotoxicity, we studied the effects of Mn on reactive oxygen species (ROS) formation, changes in high-energy phosphates (HEP), neuroinflammation mediators and associated neuronal dysfunctions both in vitro and in vivo. Primary cortical neuronal cultures showed concentration-dependent alterations in biomarkers of oxidative damage, F{sub 2}-isoprostanes (F{sub 2}-IsoPs) and mitochondrial dysfunction (ATP), as early as 2 h following Mn exposure. Treatment of neurons with 500 {mu}M Mn also resulted in time-dependent increases in the levels of the inflammatory biomarker, prostaglandin E{sub 2} (PGE{sub 2}). In vivo analyses corroborated these findings, establishing that either a single or three (100 mg/kg, s.c.) Mn injections (days 1, 4 and 7) induced significant increases in F{sub 2}-IsoPs and PGE{sub 2} in adult mouse brain 24 h following the last injection. Quantitative morphometric analyses of Golgi-impregnated striatal sections from mice exposed to single or three Mn injections revealed progressive spine degeneration and dendritic damage of medium spiny neurons (MSNs). These findings suggest that oxidative stress, mitochondrial dysfunction and neuroinflammation are underlying mechanisms in Mn-induced neurodegeneration.

  7. Photosynthetic water oxidation: insights from manganese model chemistry.

    PubMed

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(?-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2?-terpyridine), a mixed-valent di-?-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the ?-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for ?-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond-forming mechanism. Comparison between the OEC and the Mn-terpy dimer indicates that challenges remain in the development of synthetic Mn water-oxidation catalysts. These include redox leveling to couple multielectron reactions with one-electron steps, avoiding labile Mn(II) species during the catalytic cycle, and protecting the catalyst active site from undesired side reactions. As the first example of a functional manganese O2-evolution catalyst, the Mn-terpy dimer exemplifies the interrelatedness of biomimetic chemistry with biophysical studies. The design of functional model complexes enriches the study of the natural photosynthetic system, while biology continues to provide inspiration for artificial photosynthetic technologies to meet global energy demand. PMID:25730258

  8. New nanocrystalline manganese oxides as cathode materials for lithium batteries : electron microscopy, electrochemical and X-ray absorption studies

    E-print Network

    Paris-Sud XI, Université de

    1 New nanocrystalline manganese oxides as cathode materials for lithium batteries : electron.F. Abstract New nanostructured manganese oxi-iodides were prepared by redox reaction of sodium permanganate structure of these compounds, which contain octahedrally coordinated manganese atoms. The electrochemical

  9. Water-oxidation catalysis by synthetic manganese oxides--systematic variations of the calcium birnessite theme.

    PubMed

    Frey, Carolin E; Wiechen, Mathias; Kurz, Philipp

    2014-03-21

    Layered manganese oxides from the birnessite mineral family have been identified as promising heterogeneous compounds for water-oxidation catalysis (WOC), a key reaction for the conversion of renewable energy into storable fuels. High catalytic rates were especially observed for birnessites which contain calcium as part of their structures. With the aim to systematically improve the catalytic performance of such oxide materials, we used a flexible synthetic route to prepare three series of calcium birnessites, where we varied the calcium concentrations, the ripening times of the original precipitates and the temperature of the heat treatment following the initial synthetic steps (tempering) during the preparation process. The products were carefully analysed by a number of analytical techniques and then probed for WOC activity using the Ce(4+)-system. We find that our set of twenty closely related manganese oxides shows large, but somewhat systematic alterations in catalytic rates, indicating the importance of synthesis parameters for maximum catalytic performance. The catalyst of the series for which the highest water-oxidation rate was found is a birnessite of medium calcium content (Ca?:?Mn ratio 0.2?:?1) that had been subjected to a tempering temperature of 400 °C. On the basis of the detailed analysis of the results, a WOC reaction scheme for birnessites is proposed to explain the observed trends in reactivity. PMID:24225769

  10. Morphology of graphite-supported iron-manganese catalyst particles: Formation of hollow spheres during oxidation

    SciTech Connect

    Chen, A.A.; Vannice, M.A.; Phillips, J. (Pennsylvania State Univ., University Park (USA))

    1989-04-01

    Transmission electron microscopy (TEM) and Moessbauer spectroscopy (MES) were used to study the morphology of graphite-supported iron-manganese particles. Following oxidation at 500 K MES showed the iron in the particles to be fully oxidized. TEM showed all the particles to be torroidal in appearance. However, tilting resulting in no change in the apparent dimensions of the particles, yet the apparent distances between particles were sharply reduced. These results suggest the particles are actually spherical. On the basis of these experiments, and similar experiments with reduced particles, a model was developed: Following reduction the particles are spherical and consist of a metallic iron core surrounded by a shell of manganese oxide. During oxidation, iron ions diffuse through the manganese oxide shell to the particle surface. Eventually, this results in the formation of nearly spherical particles with hollow centers, inner shells of iron-manganese spinel, and outer shells of iron oxide. Upon an additional reduction the hollow center remains, but the shells phase segregate into regions of iron metal and manganese oxide.

  11. Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using Quick X-Ray Absorption Fine Structure Spectroscopy (Q-Thursday, November 5, 2009: 9:30 AM

    E-print Network

    Sparks, Donald L.

    Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using Quick X-Ray Absorption Fine, the initial rates of Cr(III) oxidation on hydrous manganese oxide (HMO) were measured at three different p

  12. Alcohol-assisted room temperature synthesis of different nanostructured manganese oxides and their pseudocapacitance properties in neutral electrolyte

    NASA Astrophysics Data System (ADS)

    Subramanian, V.; Zhu, Hongwei; Wei, Bingqing

    2008-03-01

    Different nanostructured manganese oxides have been synthesized by a simple precipitation technique using KMnO 4 and different alcohols. The synthesized manganese oxides were extensively studied using TEM, XRD, XPS, surface area measurements and electrochemical studies. TEM observations showed a range of nanostructures from nanowiskers to nanoparticles. This synthesis method promises the tuning of electronic and structural properties of the nanostructured manganese oxides by simply varying the alcohols used in the reactions. MnO 2 shows more whisker-like morphology while the Mn 2O 3 shows particle morphology. The nanostructured manganese oxides showed excellent performance as a pseudocapacitor electrode in a neutral electrolyte.

  13. Gold or silver deposited on layered manganese oxide: a functional model for the water-oxidizing complex in photosystem II.

    PubMed

    Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Sedigh, Davood Jafarian; Carpentier, Robert; Eaton-Rye, Julian J; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2013-11-01

    In this report, gold or silver deposited on layered manganese oxide has been synthesized by a simple method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, atomic absorption spectroscopy, and energy-dispersive X-ray mapping. The gold deposited on layered manganese oxide showed efficient catalytic activity toward water oxidation in the presence of cerium(IV) ammonium nitrate. The properties associated with this compound suggest it is a functional model for the water-oxidizing complex in photosystem II. PMID:23896796

  14. Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

    PubMed

    Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

    2014-09-20

    Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation and persistence of reactive Mn oxides. PMID:25079661

  15. Chemistry of a high-oxidation-level manganese porphyrin in aqueous solution

    SciTech Connect

    Spreer, L.O.; Leone, A.; Maliyackel, A.C.; Otvos, J.W.; Calvin, M.

    1988-07-13

    Manganese(III) tetrakis(N-methyl-4-pyridiniumyl)porphyrin (Mn/sup III/P/sup +/) (chloride salt) and other water-soluble manganese(III) porphyrins undergo facile one-electron electrochemical or chemical oxidation in alkaline solution. Best available evidence indicates that the final oxidized species is a manganese(IV) /mu/-oxo dimer, PMn/sup IV/-O-Mn/sup IV/P/sup 2+/. This same species is also produced by the reaction of manganese(II) porphyrin and oxygen. The Mn(IV) /mu/-oxo dimer has limited stability in water returning to 90-94% of the original Mn(III) porphyrin. The rate of this reaction is pH dependent with faster rates at lower pH. Oxygen is not produced during this reduction process. Rather, the reaction involves an unusual disproportionation in which a small percentage of the porphyrin macrocycles supply multiple electrons to rescue the remainder of the oxidized dimer. It was also found that the manganese(IV) dimer reacts rapidly with water-soluble olefins as it also does in aprotic solvent. A mechanism for the disproportionation reaction is discussed with a rate-determining step involving rearrangement of charge within the symmetric dimer to one with both oxidation equivalents on one metalloporphyrin unit, viz., PMn/sup IV/-O-Mn/sup III/P/sup +/ or PMn/sup III/-O-Mn/sup III/P/sup 2+/. This species undergoes nucleophilic attach by water or hydroxide, producing an isoporphyrin or bilirubin type molecule that has many olefinic bonds capable of reaction with remaining Mn(IV) /mu/-oxo dimer. Since coordination by OH/sup /minus// to the manganese center favors the higher manganese(IV) oxidation level, the pH dependence of the disproportionation can be explained by rearrangement within the dimer to a porphyrin-centered oxidation site. 24 references, 3 figures.

  16. Plutonium and americium sorption from an EDTA complex by manganese oxide

    SciTech Connect

    Kasper, R.B.; Delegard, C.H.

    1984-01-01

    Studies at Oak Ridge National Laboratory indicate that trace quantities of certain actinide elements are migrating from waste disposal trenches in part as Ethylenediaminetetraacetic Acid (EDTA) complexes. Some of the strongest actinide complexes are formed by EDTA and related chelating agents. To some extent, the actinides are sorbed by the soil and a positive correlation is observed between the concentration of manganese on the surface of the soil particles and the concentration of the sorbed actinides. While manganese oxides have long been recognized as important scavengers of trace metals in the environment, sorption of an actinide element from a strong chelated complex has not been previously indicated. Batch experiments were performed to evaluate the sorption of a plutonium-EDTA complex by manganese oxide. The manganese oxide was prepared as an amorphous coating on synthetic fibers following the procedure of Moore. The prepared fiber was contacted by several nitrate solutions containing different concentrations of calcium, sodium, and EDTA to evaluate the effect of competing cations, ionic strength of solution, and concentration of complexing agent. All solutions were spiked with approximately 10/sup -7/ molar of /sup 238/Pu. For all solutions, generally greater than 95% of the plutonium was sorbed by the manganese oxide-coated fibers after contact times of 10 minutes. In all cases using the manganese oxide-coated fibers, after 100 minutes of contact time, greater than 99% of the plutonium was removed from solution. For one experiment using a solution spiked with approximately 10/sup -7/ molar of /sup 241/Am, sorption of americium was found to be significantly slower than sorption of plutonium. Greater than 99% of the americium was removed from the solution only after approximately 10,000 minutes. Although the mechanism has not been established, manganese oxide was shown to sorb plutonium and americium from, or as, an EDTA complex. 22 references, 5 figures.

  17. Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves

    SciTech Connect

    Krishnan, V.V.; Suib, S.L. [Univ. of Connecticut, Storrs, CT (United States)] [Univ. of Connecticut, Storrs, CT (United States)

    1999-06-10

    Steady state kinetic studies of the oxidative dehydrogenation of 1-butene to 1,3-butadiene have been carried out on manganese oxide octahedral molecular sieve (OMS) and octahedral layered (OL) materials. Process parameters such as temperature, feed composition of 1-butene and oxygen, and feed flow rates were varied to study their effect on the activity and selectivity toward the oxidative dehydrogenation process. In addition to process parameters, modifications in the catalyst such as the ion-exchange of tunnel cations and framework substitution of manganese cations were also implemented in order to observe their effects on catalytic activity and the selectivity of 1,3-butadiene production. The ion-exchanged OMS and OL materials showed rapid deactivation with time when subjected to reaction mixtures of 1% 1-butene/0.7% oxygen/Ar and 1% 1-butene/1.1% oxygen/Ar at reaction temperatures greater than 400 C. Their selectivity toward 1,3-butadiene were typically from 15--20% (yield of 4--6%). The other products were cis and trans 2-butene and carbon dioxide and water (40--60% selectivity). Much of the oxidation was therefore nonselective. XRD data have shown that there is a phase change of the original precursor to a mixture of Mn{sub 3}O{sub 4}/MnO or plain MnO, in some cases after exposing the catalyst to reaction conditions for about 1--2 h. Framework substitution of some of the manganese with copper (OMS and OL), however, has led to higher yields and selectivities toward 1,3-butadiene. [Cu] OL-1 showed a yield of 11.8% and a maximum selectivity of 26% toward 1,3-butadiene. [Cu] OMS-1 shows a dramatically high selectivity of 36% and a yield of 11% toward 1,3-butadiene. The effect of framework substitution seems to also impede the phase change to Mn{sub 3}O{sub 4} (Hausmannite). The TPR spectra also show an increase in the lattice oxygen peak by about 40 C, in comparison with ion-exchanged OMS. This is sufficient indication that framework substitution of manganese by copper, partially, has enhanced the stability of the catalyst and improved its capacity for selective oxidation.

  18. Directed vapor deposition of lithium manganese oxide films

    NASA Astrophysics Data System (ADS)

    Jin, Sang-Wan

    Electron beam evaporation and sputtering techniques are used to fabricate multilayered thin film structures. However, these techniques suffer several drawbacks resulting from (i) the complex chemistries of the lithiated oxide layers used for the cathode and electrolyte, (ii) the need for precise microstructure control in systems with many metastable phases, and (iii) the low deposition rate and poor material utilization efficiency, which slows the application of this energy storage approach. This dissertation has investigated the use of a novel electron-beam directed vapor deposition (EB-DVD) method for the synthesis of thin film batteries. The dissertation focuses upon the cathode layer of a representative Li-ion thin film battery system and investigates in detail the deposition of lithium manganese oxide films. Many phases with offering various electrochemical performance exist in the Li-Mn-O system and the thesis also investigates the use of processing conditions to control the structure and composition of these cathode layers. In the EB-DVD approach, a high voltage electron beam is used to evaporate a source material in the throat of a nozzle that forms a coaxial transonic gas jet around the vapor. The gas jet entrains and transports the vapor to a substrate where the deposition occurs. Directed simulation of Monte Carlo (DSMC) methods indicated that the vapor plume could be matched to a substrate diameter, and the deposition rate (and vapor utilization efficiency) therefore controlled by adjusting the pressure ratio up and downstream of the nozzle opening in the deposition chamber, and by varying the gas jet density and speed. The highest deposition rates were obtained with a high pressure ratio and the gas jet density. These observations are found to be consistent with the experimental results. Deposition rates up to 16 nm/s could be achieved using the most effective gas entrainment conditions identified by DSMC calculation. This was about a factor of ten times higher than the deposition rate reported for the growth of this material by sputtering (1.5 nm/s) and other vapor deposition techniques. As-deposited lithium manganese oxide films grown on substrates at ambient temperature using high pressure ratios were found to have a disordered structure intermediate between that of the spinel (Fd3m) and rock-salt (Fm3m) phases. Post-annealing of the films in air led to a gradual structural ordering to the Fd3m, spinel structure (the thermodynamically stable phase in air) as the temperature increased to 700°C. The fully transformed films had a pure cubic spinel structure with a slightly manganese deficient composition, Li1+xMn2-yO4 where 0.08 texture. The change in film porosity and texture could be explained by the degree of homogeneous vapor phase clustering that was controllable by the gas jet pressure ratio. When deposition was conducted at elevated temperatures up to 700°C, films with various atomic structures could be fabricated. Films grown below 500°C contained mixtures of the orthorhombic LiMnO2 and the metastable rock-salt structures. Annealing these films in air resulted in a transformation to a single phase spinel structure. Films grown above 600°C had a single phase orthorhombic LiMnO2 structure. Post-annealing of these films in air led to mixtures of t

  19. Magnetic properties of manganese ferrites with additions of oxides of rare-earth elements

    Microsoft Academic Search

    I. N. Frantsevich; A. I. Gunchenko; L. N. Tul'chinskii

    1964-01-01

    1.The authors studied the effect of admixtures of oxides of ytrrium, lanthanum, cerium, neodymium on the magnetic properties of manganese ferrites. It is shown that this effect is not the same for various rare earth oxides, depending on their content in the ferrite and the change in its structure.2.On the basis of the experimental data obtained preliminary conclusions were drawn

  20. MAGNETIC PROPERTIES OF MANGANESE FERRITES WITH ADDITIONS OF OXIDES OF RARE EARTH ELEMENTS. (COMMUNICATION I)

    Microsoft Academic Search

    I. N. Frantsevich; A. I. Gunchenko; L. N. Tulchinskii

    1962-01-01

    The effect of admixtures of oxides of Y,. La, Ce, and Nd on the ; magnetic propenties of manganese ferrites was studied. It is shown that the ; effect is not the same for various rare-earth oxides, depending on their content ; in the ferrite and the change in its structure. On the basis of the experimental ; data obtained,

  1. Manganese oxidation in pH and O2 microenvironments produced by phytoplankton.

    PubMed

    Richardson, L L; Aguilar, C; Nealson, K H

    1988-01-01

    Pure cultures of Chlorella sp. catalyzed the oxidation of soluble Mn(II) to particulate, extracellular, manganic oxides. Manganese oxidation was dependent on photosynthetic activity: no oxidation was observed in the dark when cells were grown heterotrophically on glucose, or in the light when photosystem II was inhibited by the addition of DCMU. Manganates were not formed when media were buffered below pH 8.0, suggesting that an important driving force for manganese oxidation was the high pH resulting from photosynthesis. Field studies with minielectrodes in Oneida Lake, New York, demonstrated steep gradients of O2 and pH and the presence of particulate manganic oxides associated with pelagic aggregates of the cyanobacterium Microcystis sp. The manganese oxidation reaction apparently occurs only when photosynthesizing algae are present as dense populations that can generate microenvironments of high (>9.0) pH, either as aggregates in the pelagic zone or concentrated cell cultures in the laboratory. A large-scale transition from soluble to particulate manganese was measured in the surface waters of Oneida Lake throughout summer 1986. Removal of Mn(II) was correlated with the presence of aggregate-forming cyanobacteria that oxidize Mn(II) by the mechanism described above. PMID:11538363

  2. EFFECTS OF SOLAR RADIATION ON MANGANESE OXIDE REACTIONS WITH SELECTED ORGANIC COMPOUNDS

    EPA Science Inventory

    The effects of sunlight on aqueous redox reactions between manganese oxides (MnOx) and selected organic substances are reported. o sunlight-induced rate enhancement was observed for the MnOx oxidation of substituted phenols, anisole, o-dichlorobenzene, or p-chloroaniline. n the o...

  3. 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.

  4. Supporting information for Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using Quick Scanning X-Ray Absorption Fine Structure Spectroscopy (Q-XAFS)

    E-print Network

    Sparks, Donald L.

    S-1 Supporting information for Kinetics of Chromium(III) Oxidation by Manganese(IV) Oxides Using Summary of supporting information: Page S-1: Figure S1: HMO XRD pattern Page S-2: Figure S2- Chromium pre: Literature cited Figure S1: XRD pattern of hydrous manganese oxide. #12;S-2 Figure S2- Chromium pre

  5. A very simple method to synthesize nano-sized manganese oxide: an efficient catalyst for water oxidation and epoxidation of olefins.

    PubMed

    Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Amini, Mojtaba; Nayeri, Sara; Bagherzadeh, Mojtaba

    2012-08-28

    Nano-sized particles of manganese oxides have been prepared by a very simple and cheap process using a decomposing aqueous solution of manganese nitrate at 100 °C. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectrometry have been used to characterize the phase and the morphology of the manganese oxide. The nano-sized manganese oxide shows efficient catalytic activity toward water oxidation and the epoxidation of olefins in the presence of cerium(IV) ammonium nitrate and hydrogen peroxide, respectively. PMID:22858683

  6. THE EFFECTS OF IRON(II) ON ARSENIC(III) OXIDATION AND ARSENIC SORPTION/DESORPTION ON MANGANESE OXIDES

    E-print Network

    Sparks, Donald L.

    THE EFFECTS OF IRON(II) ON ARSENIC(III) OXIDATION AND ARSENIC SORPTION/DESORPTION ON MANGANESE © 2014 Yun Wu All Rights Reserved #12;THE EFFECTS OF IRON(II) ON ARSENIC(III) OXIDATION AND ARSENIC, Caroline Golt on arsenic speciation and UD Soil Test Lab. I thank all current and previous members

  7. Effect of respiration and manganese on oxidative stress resistance of Lactobacillus plantarum WCFS1.

    PubMed

    Watanabe, Masayuki; van der Veen, Stijn; Nakajima, Hadjime; Abee, Tjakko

    2012-01-01

    Lactobacillus plantarum is a facultatively anaerobic bacterium that can perform respiration under aerobic conditions in the presence of haem, with vitamin K2 acting as a source of menaquinone. We investigated growth performance and oxidative stress resistance of Lb. plantarum WCFS1 cultures grown in de Man, Rogosa and Sharpe (MRS) medium without and with added manganese under fermentative, aerobic, aerobic with haem, and respiratory conditions. Previous studies showed that Lb. plantarum WCFS1 lacks a superoxide dismutase and requires high levels of manganese for optimum fermentative and aerobic growth. In this study, respiratory growth with added manganese resulted in significantly higher cell densities compared to the other growth conditions, while without manganese added, similar but lower cell densities were reached. Notably, cells derived from the respiratory cultures showed the highest hydrogen peroxide resistance in all conditions tested, although similar activity levels of haem-dependent catalase were detected in cells grown under aerobic conditions with haem. These results indicate that oxidative stress resistance of Lb. plantarum is affected by respiratory growth, growth phase, haem and manganese. As levels of haem and manganese can differ considerably in the raw materials used in fermentation processes, including those of milk, meat and vegetables, the insight gained here may provide tools to increase the performance and robustness of starter bacteria. PMID:22016573

  8. Synthesis and Characterization of a Layered Manganese Oxide: Materials Chemistry for the Inorganic or Instrumental Methods Lab

    ERIC Educational Resources Information Center

    Ching, Stanton; Neupane, Ram P.; Gray, Timothy P.

    2006-01-01

    A three-week laboratory project involving synthesis and characterization of a layered manganese oxide provides an excellent vehicle for teaching important concepts of inorganic chemistry and instrumental methods related to non-molecular systems. Na-birnessite is an easily prepared manganese oxide with a 7 A interlayer spacing and Na[superscript +]…

  9. Synthesis of nanostructured manganese oxides from a dipolar binary liquid (water\\/benzene) system and hydrogen storage ability research

    Microsoft Academic Search

    Hai Men; Peng Gao; Yuzeng Sun; Yujin Chen; Xiaona Wang; Longqiang Wang

    2010-01-01

    A new dipolar binary liquid strategy has been developed to manganese oxide nanostructure’s synthesis, in which different manganese oxide nanostructures have been easily obtained without using any templates or catalysts. It has been found that the reaction temperatures, alkali precipitators’ concentrations and Mn2+ concentrations play a significant role in our dipolar binary liquid technique. This novel approach can be potentially

  10. Manganese oxide helices, rings, strands, and films, and methods for their preparation

    DOEpatents

    Suib, Steven L. (Storrs, CT); Giraldo, Oscar (Storrs, CT); Marquez, Manuel (Wheeling, IL); Brock, Stephanie (Detroit, MI)

    2003-01-07

    Methods for the preparation of mixed-valence manganese oxide compositions with quaternary ammonium ions are described. The compositions self-assemble into helices, rings, and strands without any imposed concentration gradient. These helices, rings, and strands, as well as films having the same composition, undergo rapid ion exchange to replace the quaternary ammonium ions with various metal ions. And the metal-ion-containing manganese oxide compositions so formed can be heat treated to form semi-conducting materials with high surface areas.

  11. Hyperthermia HeLa cell treatment with silica coated manganese oxide nanoparticles

    E-print Network

    Villanueva, A; Alonso, JM; Rueda, T; Martínez, A; Crespo, P; Morales, MP; Fernandez, MA Gonzalez; Valdes, J; Rivero, G

    2009-01-01

    HeLa tumour cells incubated with ferromagnetic nanoparticles of manganese oxide perovskite La0.56(SrCa)0.22MnO3 were treated with a high frequency alternating magnetic field. The particles were previously coated with silica to improve their biocompatibility. The control assays made with HeLa tumour cells showed that cell survival and growth rate were not affected by the particle internalization in cells, or by the electromagnetic field on cells without nanoparticles. The application of an alternating electromagnetic field to cells incubated with this silica coated manganese oxide induced a significant cellular damage that finally lead to cell death by an apoptotic mechanism.

  12. Manganese Oxidation In A Natural Marine Environment- San Antonio Bay

    E-print Network

    Neyin, Rosemary Ogheneochuko

    2013-04-12

    Cosmochimica Acta 54(3): 781-795. Brewer P.G., Spencer D.W. 1971. Colorimetric Determination of Manganese in Anoxic Waters. Limnology and Oceanography 16(1): 107-110. Brouwers G., De Vrind J.P.M., Corstjens P.L.A.M., Cornelis P., Baysse C., De Vrind- De... ............................................................................................................... 1 STUDY AREA .................................................................................................................... 4 METHODS...

  13. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis

    NASA Astrophysics Data System (ADS)

    Li, Cheng-Shiuan; Melaet, Gérôme; Ralston, Walter T.; An, Kwangjin; Brooks, Christopher; Ye, Yifan; Liu, Yi-Sheng; Zhu, Junfa; Guo, Jinghua; Alayoglu, Selim; Somorjai, Gabor A.

    2015-03-01

    Carbon dioxide capture and use as a carbon feedstock presents both environmental and industrial benefits. Here we report the discovery of a hybrid oxide catalyst comprising manganese oxide nanoparticles supported on mesoporous spinel cobalt oxide, which catalyses the conversion of carbon dioxide to methanol at high yields. In addition, carbon–carbon bond formation is observed through the production of ethylene. We document the existence of an active interface between cobalt oxide surface layers and manganese oxide nanoparticles by using X-ray absorption spectroscopy and electron energy-loss spectroscopy in the scanning transmission electron microscopy mode. Through control experiments, we find that the catalyst’s chemical nature and architecture are the key factors in enabling the enhanced methanol synthesis and ethylene production. To demonstrate the industrial applicability, the catalyst is also run under high conversion regimes, showing its potential as a substitute for current methanol synthesis technologies.

  14. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis.

    PubMed

    Li, Cheng-Shiuan; Melaet, Gérôme; Ralston, Walter T; An, Kwangjin; Brooks, Christopher; Ye, Yifan; Liu, Yi-Sheng; Zhu, Junfa; Guo, Jinghua; Alayoglu, Selim; Somorjai, Gabor A

    2015-01-01

    Carbon dioxide capture and use as a carbon feedstock presents both environmental and industrial benefits. Here we report the discovery of a hybrid oxide catalyst comprising manganese oxide nanoparticles supported on mesoporous spinel cobalt oxide, which catalyses the conversion of carbon dioxide to methanol at high yields. In addition, carbon-carbon bond formation is observed through the production of ethylene. We document the existence of an active interface between cobalt oxide surface layers and manganese oxide nanoparticles by using X-ray absorption spectroscopy and electron energy-loss spectroscopy in the scanning transmission electron microscopy mode. Through control experiments, we find that the catalyst's chemical nature and architecture are the key factors in enabling the enhanced methanol synthesis and ethylene production. To demonstrate the industrial applicability, the catalyst is also run under high conversion regimes, showing its potential as a substitute for current methanol synthesis technologies. PMID:25754475

  15. Cobalt(II) Oxidation by the Marine Manganese(II)-Oxidizing Bacillus sp. Strain SG-1

    PubMed Central

    Lee, Yoon; Tebo, Bradley M.

    1994-01-01

    The geochemical cycling of cobalt (Co) has often been considered to be controlled by the scavenging and oxidation of Co(II) on the surface of manganese [Mn(III,IV)] oxides or manganates. Because Mn(II) oxidation in the environment is often catalyzed by bacteria, we have investigated the ability of Mn(II)-oxidizing bacteria to bind and oxidize Co(II) in the absence of Mn(II) to determine whether some Mn(II)-oxidizing bacteria also oxidize Co(II) independently of Mn oxidation. We used the marine Bacillus sp. strain SG-1, which produces mature spores that oxidize Mn(II), apparently due to a protein in their spore coats (R.A. Rosson and K. H. Nealson, J. Bacteriol. 151:1027-1034, 1982; J. P. M. de Vrind et al., Appl. Environ. Microbiol. 52:1096-1100, 1986). A method to measure Co(II) oxidation using radioactive 57Co as a tracer and treatments with nonradioactive (cold) Co(II) and ascorbate to discriminate bound Co from oxidized Co was developed. SG-1 spores were found to oxidize Co(II) over a wide range of pH, temperature, and Co(II) concentration. Leucoberbelin blue, a reagent that reacts with Mn(III,IV) oxides forming a blue color, was found to also react with Co(III) oxides and was used to verify the presence of oxidized Co in the absence of added Mn(II). Co(II) oxidation occurred optimally around pH 8 and between 55 and 65°C. SG-1 spores oxidized Co(II) at all Co(II) concentrations tested from the trace levels found in seawater to 100 mM. Co(II) oxidation was found to follow Michaelis-Menten kinetics. An Eadie-Hofstee plot of the data suggests that SG-1 spores have two oxidation systems, a high-affinity-low-rate system (Km, 3.3 × 10-8 M; Vmax, 1.7 × 10-15 M · spore-1 · h-1) and a low-affinity-high-rate system (Km, 5.2 × 10-6 M; Vmax, 8.9 × 10-15 M · spore-1 · h-1). SG-1 spores did not oxidize Co(II) in the absence of oxygen, also indicating that oxidation was not due to abiological Co(II) oxidation on the surface of preformed Mn(III,IV) oxides. These results suggest that some microorganisms may directly oxidize Co(II) and such biological activities may exert some control on the behavior of Co in nature. SG-1 spores may also have useful applications in metal removal, recovery, and immobilization processes. Images PMID:16349360

  16. SERUM CHEMISTRIES OF COTURNIX JAPONICA GIVEN DIETARY MANGANESE OXIDE (MN3O4)

    EPA Science Inventory

    Plasma creatinine and inorganic phosphorus were increased in manganese oxide (Mn3O4)-treated adult male Coturnix quail, but BUN, BUN/creatinine ratio, uric acid, and total calcium were decreased. 2. Serum enzymes (alkaline phosphatase glutamic oxaloacetic transaminase, glutamic p...

  17. Structural study of biotic and abiotic poorly-crystalline manganese oxides using atomic

    E-print Network

    Sparks, Donald L.

    Structural study of biotic and abiotic poorly-crystalline manganese oxides using atomic pair structures. In this study, the crystal structures of their synthetic analogs includ- ing acid birnessite using atomic pair distribution function (PDF) analysis. Results unambiguously verify that these Mn

  18. Nanostructural evolution from nanosheets to one-dimensional nanoparticles for manganese oxide

    SciTech Connect

    Pan, Hongmei [Department of Preparatory Education, Guangxi University for Nationalities, Daxuexi-Road 188, Nanning, Guangxi 530006 (China)] [Department of Preparatory Education, Guangxi University for Nationalities, Daxuexi-Road 188, Nanning, Guangxi 530006 (China); Kong, Xingang [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan)] [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan); Wen, Puhong [Department of Chemistry and Chemical Engineering, Baoji University of Arts and Science, 1 Gaoxin Road, Baoji, Shaanxi 721013 (China)] [Department of Chemistry and Chemical Engineering, Baoji University of Arts and Science, 1 Gaoxin Road, Baoji, Shaanxi 721013 (China); Kitayama, Tomonori [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan)] [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan); Feng, Qi, E-mail: feng@eng.kagawa-u.ac.jp [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan)] [Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396 (Japan)

    2012-09-15

    Highlights: ? Nanosheets were transformed to other one-dimensional nanoparticles. ? Nanofibers, nanotubes, nanoribbons, and nanobelts were obtained. ? Nanoparticle morphology can be controlled with organic amines. ? Organic amines act as morphology directing agent. -- Abstract: This paper introduces a novel hydrothermal soft chemical synthesis process for manganese oxide nanostructured particles using two-dimensional manganese oxide nanosheets as precursor. In this process, a birnessite-type manganese oxide with a layered structure was exfoliated into its elementary layer nanosheets, and then the nanosheets were hydrothermally treated to transform the two-dimensional morphology of the nanosheets to one-dimensional nanoparticles. The manganese oxide nanofibers, nanotubes, nanobelts, nanoribbons, and fabric-ribbon-like particles constructed from nanofibers or nanobelts were obtained using this hydrothermal soft chemical process. The nanostructural evolution from the two-dimensional nanosheets to the one-dimensional nanoparticles was characterized by XRD, SEM, TEM, and TG-DTA analysis. The morphology and nanostructure of the products are strongly dependent on the molecular dimension of organic amine cations added in the reaction system. The organic amine cations act as a morphology directing agent in the nanostructural evolution process.

  19. Manganese oxide micro-supercapacitors with ultra-high areal capacitance

    NASA Astrophysics Data System (ADS)

    Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

    2013-05-01

    A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 ?A cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 ?A cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

  20. Diclofenac and 2?anilinophenylacetate degradation by combined activity of biogenic manganese oxides and silver

    PubMed Central

    Meerburg, Francis; Hennebel, Tom; Vanhaecke, Lynn; Verstraete, Willy; Boon, Nico

    2012-01-01

    Summary The occurrence of a range of recalcitrant organic micropollutants in our aquatic environment has led to the development of various tertiary wastewater treatment methods. In this study, biogenic manganese oxides (Bio?MnOx), biogenic silver nanoparticles (Bio?Ag0) and ionic silver were used for the oxidative removal of the frequently encountered drug diclofenac and its dechlorinated form, 2?anilinophenylacetate (APA). Diclofenac was rapidly degraded during ongoing manganese oxidation by Pseudomonas putida MnB6. Furthermore, whereas preoxidized Bio?MnOx, Bio?Ag0 and Ag+ separately did not show any removal capacity for diclofenac, an enhanced removal occurred when Bio?MnOx and silver species were combined. Similar results were obtained for APA. Finally, a slow removal of diclofenac but more rapid APA degradation was observed when silver was added to manganese?free P.?putida biomass. Combining these results, three mechanisms of diclofenac and APA removal could be distinguished: (i) a co?metabolic removal during active Mn2+ oxidation by P.?putida; (ii) a synergistic interaction between preoxidized Bio?MnOx and silver species; and (iii) a (bio)chemical process by biomass enriched with silver catalysts. This paper demonstrates the use of P.?putida for water treatment purposes and is the first report of the application of silver combined with biogenic manganese for the removal of organic water contaminants. PMID:22221449

  1. Synthesis of nanostructured manganese oxides based materials and application for supercapacitor

    NASA Astrophysics Data System (ADS)

    Dung Dang, Trung; Le, Thi Thu Hang; Bich Thuy Hoang, Thi; Mai, Thanh Tung

    2015-01-01

    Manganese oxides are important materials with a variety of applications in different fields such as chemical sensing devices, magnetic devices, field-emission devices, catalysis, ion-sieves, rechargeable batteries, hydrogen storage media and microelectronics. To open up new applications of manganese oxides, novel morphologies or nanostructures are required to be developed. Via sol—gel and anodic electrodeposition methods, M (Co, Fe) doped manganese oxides were prepared. On the other hand, nanostructured (nanoparticles, nanorods and hollow nanotubes) manganese oxides were synthesized via a process including a chemical reaction with carbon nanotubes (CNTs) templates followed by heat treatment. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV) and impedance spectroscopy (EIS) were used for characterization of the prepared materials. The influence of chemical reaction conditions, heat treatment and template present on the morphology, structure, chemical and electrochemical properties of the prepared materials were investigated. Chronopotentiometry (CP) and CV results show high specific capacitance of 186.2 to 298.4 F g?1 and the charge/discharge stability of the prepared materials and the ideal pseudocapacitive behaviors were observed. These results give an opening and promising application of these materials in advanced energy storage applications.

  2. Manganese deposits on Mars suggest a highly oxidized past

    NASA Astrophysics Data System (ADS)

    Rosen, Julia

    2014-11-01

    As the Curiosity rover picks its way across the Martian surface, sampling rocks and snapping photos, it searches for signs that the dusty craters and ridges under its treads may once have supported life or, at least, that they might have been habitable. Now, using measurements of manganese abundances in Martian rocks, Lanza et al. provide new evidence that Mars may have hosted liquid water and a more strongly oxygenated atmosphere at some point in its past.

  3. Coexistence of electrical conductivity and ferromagnetism in a hybrid material formed from reduced graphene oxide and manganese oxide.

    PubMed

    Murashima, Yusuke; Ohtani, Ryo; Matsui, Takeshi; Takehira, Hiroshi; Yokota, Ryotaro; Nakamura, Masaaki; Lindoy, Leonard F; Hayami, Shinya

    2015-03-01

    The coexistence of electrical conductivity and ferromagnetism has been achieved in a reduced graphene oxide/manganese oxide hybrid (rGO-Mn) synthesized by chemical reduction of a graphene oxide and Mn(2+) (as its GO-Mn(2+) complex) using hydrazine. The rGO-Mn and GO-Mn(2+) complexes were characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). In rGO-Mn the Mn was present as manganese oxide nanoparticles located on the rGO nanosheets. This rGO-Mn exhibits both electrical conductivity and ferromagnetism. The synthesis of hybrids incorporating rGO and metal oxides is proposed as a useful strategy for generation of new multifunctional nano-composite materials. PMID:25697449

  4. Endowing manganese oxide with fast adsorption ability through controlling the manganese carbonate precursor assembled in ionic liquid.

    PubMed

    Ge, X; Gu, C D; Wang, X L; Tu, J P

    2015-01-15

    Manganese oxides with desired structure are controllably obtained through annealing MnCO3 precursors with required structures. The structures of MnCO3 precursors are determined by a "mesocrystal formation" process in an ionic liquid system of a choline chloride/urea (CU) mixture. Without addition of surfactants, only CU solvent and manganese chloride are needed in the reaction system, in which the CU acts as reaction medium as well as control agent for particle growth. A shape transformation of MnCO3 particles from well-defined rhombohedral mesocrystals to ellipsoidal polycrystal ensembles, and to nanoparticulate aggregates is observed when heating the reaction system for 4 h at 120, 150, and 180 °C, respectively. With a longer aging time at 120 °C, etching and disassembly of MnCO3 mesocrystals happened. The correlation between the microstructure and the underlying formation mechanism is highlighted. Porous and nanowire-like MnO(x) nanostructures are obtained through a facile thermal conversion process from the diverse MnCO3 precursors, which are demonstrated as effective and efficient adsorbents to remove organic waste (e.g. Congo red) from water. Significantly, the nanowire-like MnO(x) nanostructures obtained by annealing the MnCO3 mesocrystals at 300 °C for 4 h can remove about 95% Congo red in waste water at room temperature in only one minute, which is superior to the reported hierarchical hollow nanostructured MnO2. PMID:25454437

  5. Processing of Manganese-Doped [Bi0.5Na0.5]TiO3 Ferroelectrics: Reduction and Oxidation Reactions During Calcination and Sintering

    E-print Network

    McQuade, D. Tyler

    Processing of Manganese-Doped [Bi0.5Na0.5]TiO3 Ferroelectrics: Reduction and Oxidation Reactions The effect of multivalent manganese doping on the defect struc- ture is studied for the ``lead) spectroscopy. The results show that manganese is incorporated with di- and trivalent oxidation states

  6. Electrodeposition of layered manganese oxide nanocomposites intercalated with strong and weak polyelectrolytes.

    PubMed

    Nakayama, Masaharu; Tagashira, Hiroki

    2006-04-11

    Multilayered manganese oxide nanocomposites intercalated with strong (poly(diallyldimethylammonium) chloride, PDDA) and weak (poly(allylamine hydrochloride), PAH) polyelectrolytes can be produced on polycrystalline platinum electrode in a thin film form by a simple, one-step electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn2+ ions at around +1.0 V (vs Ag/AgCl) in the presence of polyelectrolytes. Fully charged PDDA polycations are accommodated tightly in the interlayer space by electrostatic interaction with negative charges on the manganese oxide layers, leading to an interlayer distance of 0.97 nm. The layered film prepared with PAH has a larger polymer content (PAH/Mn molar ratio of 0.98) than that (PDDA/Mn molar ratio of 0.43) made with PDDA because of the smaller charging degree of PAH, exhibiting a larger interlayer distance (1.19 nm). The interlayer PAH contains neutral (-NH2) and positively charged (-NH3(+)) amine groups, and the -NH3(+) groups are associated with Cl- (to generate -NH3(+) Cl- ion pairs) as well as the negatively charged manganese oxide layers. Both polyelectrolytes once incorporated were not ion exchanged with small cations in solution. The layered structure of PDDA/MnO(x) was collapsed during the reduction process in a KCl electrolyte solution, accompanying an expansion of the interlayer as a result of incorporation of K+ ions for charge neutrality. On the contrary, the layered PAH/MnO(x) film showed a good electrochemical response due to the redox reaction of Mn3+/Mn4+ couple with no change in the structure. X-ray photoelectron spectroscopy revealed that, in this case, excess negative charges generated on the manganese oxide layers upon reduction can be balanced by the protons being released from the -NH3(+) Cl- sites in the interlayer PAH; the Cl- anions becoming unnecessary are inevitably excluded from the interlayer, and vice versa upon oxidation. PMID:16584268

  7. Thursday, November 8, 2007 -10:50 AM Kinetics of Chromium(III) Oxidation on Manganese Oxides Using Real-Time Molecular Scale Approaches.

    E-print Network

    Sparks, Donald L.

    Thursday, November 8, 2007 - 10:50 AM 343-3 Kinetics of Chromium(III) Oxidation on Manganese Oxides capable of oxidizing chromium(III) to the more hazardous and mobile chromium(VI). Although the kinetics of chromium oxidation by Mn-oxides have been studied, the calculated rate parameters are apparent since

  8. Tailoring structural, optical and magnetic properties of spinel type cobalt oxide (Co3O4) by manganese doping

    NASA Astrophysics Data System (ADS)

    Naveen, A. Nirmalesh; Selladurai, Subramanian

    2015-01-01

    To study the effects of manganese doping on structural, optical and magnetic properties of spinel type cobalt oxide (Co3O4) system, manganese ions were doped at different concentrations (5-20%) using co-precipitation method. Crystalline nature and phase purity of the prepared materials were investigated using XRD, FTIR and XPS measurements. Manganese ions played a major role in reducing crystallite size and introducing macro/micro-strains in the doped compounds. Surface morphology of the materials examined using FESEM images confirmed the role played by manganese ion in restraining particle growth. Manganese doping was further confirmed using EDS and XPS elemental analysis. From the XPS studies, manganese concentration in the doped samples were identified to be close to the initial doping percentage (MnxCo3-xO4; x=4.61%, 8.25%, 14.13% and 18.10%). Presence of three types of manganese ions was revealed from the XPS study. Pair of absorption bands centered at 440 nm and 720 nm characteristic of spinel type cobalt oxide was observed for all the prepared materials. Micro- and macro-strains induced by manganese doping have created localized density of states reducing band energy gaps in the doped materials. Mn2+ ions replacing Co2+ ions in the tetrahedral site have enhanced the weak ferromagnetism observed for pristine cobalt oxide. Saturation magnetization, coercivity and remanent magnetization was found to increase with Mn2+ concentration.

  9. Uraninite oxidation and dissolution induced by manganese oxide: A redox reaction between two insoluble minerals

    NASA Astrophysics Data System (ADS)

    Wang, Zimeng; Lee, Sung-Woo; Kapoor, Pratyul; Tebo, Bradley M.; Giammar, Daniel E.

    2013-01-01

    The longevity of subsurface U(IV) produced by reduction of U(VI) during in situ bioremediation can be limited by reoxidation to more mobile U(VI) species. Coupling of the biogeochemical cycles of U and Mn may affect the fate and transport of uranium. Manganese oxides can act as a powerful oxidant that accelerates the oxidative dissolution of UO2. This study investigated the physical and chemical factors controlling the interaction between UO2 and MnO2, which are both poorly soluble minerals. A multi-chamber reactor with a permeable membrane was used to eliminate direct contact of the two minerals while still allowing transport of aqueous species. The oxidation of UO2 was not significantly enhanced by MnO2 if the two solids were physically separated. Complete mixing of MnO2 with UO2 led to a much greater extent and rate of U oxidation. When direct contact is not possible, the reaction slowly progresses through release of soluble U(IV) with its adsorption and oxidation on MnO2. Continuously-stirred tank reactors (CSTRs) were used to quantify the steady-state rates of UO2 dissolution induced by MnO2. MnO2 dramatically promoted UO2 dissolution, but the degree of promotion leveled off once the MnO2:UO2 ratio exceeded a critical value. Substantial amounts of U(VI) and Mn(II) were retained on MnO2 surfaces. The total production of Mn(II) was less than that of U(VI), indicating that the fate of Mn products and their impact on UO2-MnO2 reaction kinetics were complicated and may involve formation of Mn(III) phases. At higher dissolved inorganic carbon concentrations, UO2 oxidation by MnO2 was faster and less U(VI) was adsorbed to MnO2. Such an inverse relationship suggested that U(VI) may passivate MnO2 surfaces. A conceptual model was developed to describe the oxidation rate of UO2 by MnO2. This model is potentially applicable to a broad range of water chemistry conditions and is relevant to other environmental redox processes involving two poorly soluble minerals.

  10. Electroless preparation and ASAXS microstructural analysis of pseudocapacitive carbon manganese oxide supercapacitor electrodes.

    PubMed

    Weber, Christian; Reichenauer, Gudrun; Pflaum, Jens

    2015-01-20

    Anomalous small angle X-ray scattering (ASAXS) has been utilized as a noninvasive, integral tool to access the structural properties of carbon xerogel-manganese oxide electrodes with nanometer resolution. As these electrodes constitute the elementary functional units in supercapacitors and as their microstructure governs the macroscopic electrical performance, it is essential to gain a detailed morphological understanding of the underlying carbon particle scaffold coated with manganese oxide. We demonstrate that, in this regard, ASAXS provides a powerful technique and in combination with a theoretical core-shell model enables a quantitative estimation of the relevant structural parameters. As a result, we determined the thicknesses of the solution deposited MnO2 shells to range between 3 and 26 nm depending on the carbon particle size and thus on their effective surface area. By our core-shell modeling we conclude the revealed manganese oxide coatings on the carbon support to be rather thick, but nevertheless to show a high uniformity in thickness. At 1.8 ± 0.2 to 2.2 ± 0.1 g/cm(3) the related effective MnO2 densities of the shells are about 30% lower than the corresponding bulk density of 3.0 g/cm(3). This mainly originates from a substructure within the shell, whose growth is controlled by a pronounced reduction of the manganese precursor during layer formation. Finally, the presented ASAXS data are complemented by SEM and N2 sorption measurements, proving not only qualitatively the proposed flake-like MnO2 surface morphology but also confirming quantitatively the manganese shell thickness, complementary, on a local scale. PMID:25453192

  11. Correction: Sacrificial template-directed synthesis of mesoporous manganese oxide architectures with superior performance for organic dye adsorption

    NASA Astrophysics Data System (ADS)

    Ai, Lunhong; Yue, Haitao; Jiang, Jing

    2014-10-01

    Correction for `Sacrificial template-directed synthesis of mesoporous manganese oxide architectures with superior performance for organic dye adsorption' by Lunhong Ai et al., Nanoscale, 2012, 4, 5401-5408.

  12. Thin films of octahedral molecular sieves of manganese oxide

    SciTech Connect

    Segal, S.R.; Park, S.H.; Suib, S.L. [Univ. of Connecticut, Storrs, CT (United States)] [Univ. of Connecticut, Storrs, CT (United States)

    1997-01-01

    Octahedral layered molecular sieve materials (OL-1) having the birnessite structure have been synthesized using sol-gel preparation methods. The sol obtained by redox reaction between sucrose and KMnO{sub 4} is then used to make films via (a) immersion, (b) spray coating, (c) spin coating, and (d) spatula coating. Crystalline OL-1 thin films have been prepared by methods a-c. Thin homogeneous films are most readily prepared by spray coating. Spin coating leads to noncrystalline and manganese-deficient films. The films have been characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, and scanning Auger microscopy. The microscopy and Auger experiments show that there was no charging, implying these samples are good electrical conductors. The films are free from large amounts of impurity ions and carbonaceous deposits formed during the syntheses. 25 refs., 5 figs., 3 tabs.

  13. Protective role of silymarin against manganese-induced nephrotoxicity and oxidative stress in rat.

    PubMed

    Chtourou, Yassine; Garoui, El mouldi; Boudawara, Tahia; Zeghal, Najiba

    2014-10-01

    Metal toxicity may occur after exposure from many sources. Oxidative stress is thought to be involved in manganese-induced toxicity and leads to various health disorders. Silymarin (SIL), a natural flavonoid, has been reported to have many benefits and medicinal properties. The aim of this study was to assess the toxicity of manganese (Mn) on oxidative stress and DNA damage in the kidney of rats and its alleviation by SIL. Manganese was given orally in drinking water (20 mg MnCl2 /mL) with or without SIL administration (100 mg /kg intraperitoneally) for 30 days. Our data showed that SIL significantly prevented Mn induced nephrotoxicity, indicated by both diagnostic indicators of kidney injury like plasma urea, uric acid and creatinine and urinary electrolyte levels and by histopathological analysis. Moreover, Mn-induced profound elevation of the production of reactive oxygen species (ROS) and altered the levels of oxidative stress related biomarkers in kidney tissue. This is evidenced by the increase of lipid peroxidation, protein carbonylation, DNA fragmentation and urinary hydrogen peroxide, while, the activities of enzymatic antioxidant and glutathione level were decreased. Treatment with SIL reduced the alterations in the renal and urine markers, decreasing lipid peroxidation markers, increasing the antioxidant cascade and decreasing the Mn-induced damage. All these changes were supported by histopathological observations. These findings suggested that the inhibition of Mn-induced damage by SIL was due at least in part to its antioxidant activity and its capacity to modulate the oxidative damage. PMID:23339144

  14. Manganese oxide/carbon yolk-shell nanorod anodes for high capacity lithium batteries.

    PubMed

    Cai, Zhengyang; Xu, Lin; Yan, Mengyu; Han, Chunhua; He, Liang; Hercule, Kalele Mulonda; Niu, Chaojiang; Yuan, Zefan; Xu, Wangwang; Qu, Longbing; Zhao, Kangning; Mai, Liqiang

    2015-01-14

    Transition metal oxides have attracted much interest for their high energy density in lithium batteries. However, the fast capacity fading and the low power density still limit their practical implementation. In order to overcome these challenges, one-dimensional yolk-shell nanorods have been successfully constructed using manganese oxide as an example through a facile two-step sol-gel coating method. Dopamine and tetraethoxysilane are used as precursors to obtain uniform polymer coating and silica layer followed by converting into carbon shell and hollow space, respectively. As anode material for lithium batteries, the manganese oxide/carbon yolk-shell nanorod electrode has a reversible capacity of 660 mAh/g for initial cycle at 100 mA/g and exhibits excellent cyclability with a capacity of 634 mAh/g after 900 cycles at a current density of 500 mA/g. An enhanced capacity is observed during the long-term cycling process, which may be attributed to the structural integrity, the stability of solid electrolyte interphase layer, and the electrochemical actuation of the yolk-shell nanorod structure. The results demonstrate that the manganese oxide is well utilized with the one-dimensional yolk-shell structure, which represents an efficient way to realize excellent performance for practical applications. PMID:25490409

  15. Synthesis and Characterization of a Novel Extracellular Biogenic Manganese Oxide (Bixbyite-like Mn 2 O 3 ) Nanoparticle by Isolated Acinetobacter sp

    Microsoft Academic Search

    Baharak Hosseinkhani; Giti Emtiazi

    Recently, manganese oxides have been considered in the environmental remediation, MRI diagnosis and drug and pharmaceutical\\u000a industries. Different numbers of physicochemical and biological methods have been reported for the preparation of nanoscale\\u000a manganese oxides. Although manganese oxide biogenesis by bacterial species has been recognized as the major Mn-oxidizing agent\\u000a in nature, in this research, for first time, we demonstrated the

  16. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. (Pacific Northwest Lab., Richland, WA (United States)); Sims, R.C. (Utah State Univ., Logan, UT (United States). Dept. of Civil and Environmental Engineering)

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  17. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. [Pacific Northwest Lab., Richland, WA (United States); Sims, R.C. [Utah State Univ., Logan, UT (United States). Dept. of Civil and Environmental Engineering

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  18. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-06-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH.

  19. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    PubMed Central

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-01-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. PMID:24977746

  20. Oxidation of antimony (III) by amorphous iron and manganese oxyhydroxides

    Microsoft Academic Search

    Nelson Belzile; Yu-Wei Chen; Zijian Wang

    2001-01-01

    Amorphous forms of natural and synthetic Fe oxyhydroxides and synthetic Mn oxyhydroxides were used to study the oxidation of antimonite, Sb(III), at different pH values. Sb species were measured by differential pulse adsorptive stripping voltametry (DPACSV). The oxidation of Sb(III) to Sb(V) was always rapid and completed after a few days following pseudo-first order rate laws. A slightly slower oxidation

  1. Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

    USGS Publications Warehouse

    Buss, H.L.; Sak, P.B.; Webb, S.M.; Brantley, S.L.

    2008-01-01

    In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (???2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ??V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 A??, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 ?? 10-14 mol biotite m-2 s-1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 ??m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 ?? 10-13 mol hornblende m-2 s-1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface. ?? 2008 Elsevier Ltd. All rights reserved.

  2. Weathering of the Rio Blanco Quartz Diorite, Luquillo Mountains, Puerto Rico: Coupling Oxidation, Dissolution, And Fracturing

    SciTech Connect

    Buss, H.L.; Sak, P.B.; Webb, S.M.; Brantley, S.L.

    2009-05-12

    In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers ({approx}2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive {Delta}V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 {angstrom}, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 x 10{sup -14} mol biotite m{sup -2} s{sup -1}. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 {micro}m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 x 10{sup -13} mol hornblende m{sup -2} s{sup -1}: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O{sub 2} at the bedrock-saprolite interface.

  3. Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors

    NASA Astrophysics Data System (ADS)

    Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

    2013-10-01

    Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g-1), energy (9.0 W h kg-1), power (59.7 kW kg-1), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications.Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g-1), energy (9.0 W h kg-1), power (59.7 kW kg-1), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications. Electronic supplementary information (ESI) available: Chemical structures of functional groups on cellulose fibers, the surface water wettability of rice paper, CV curves of supercapacitors at different scan rates, galvanostatic charge-discharge curves of supercapacitors at different current densities, TGA profiles of the SWCNT-MnO2-paper composites synthesized at different temperatures, TEM images of MnO2 particles deposited on rice paper at different temperatures, photographs of supercapacitors under different bending test conditions, and a video of bending and folding the SWCNT-MnO2-paper composites. See DOI: 10.1039/c3nr03010e

  4. Low-temperature, manganese oxide-based, thermochemical water splitting cycle

    PubMed Central

    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.

    2012-01-01

    Thermochemical cycles that split water into stoichiometric amounts of hydrogen and oxygen below 1,000?°C, and do not involve toxic or corrosive intermediates, are highly desirable because they can convert heat into chemical energy in the form of hydrogen. We report a manganese-based thermochemical cycle with a highest operating temperature of 850?°C that is completely recyclable and does not involve toxic or corrosive components. The thermochemical cycle utilizes redox reactions of Mn(II)/Mn(III) oxides. The shuttling of Na+ into and out of the manganese oxides in the hydrogen and oxygen evolution steps, respectively, provides the key thermodynamic driving forces and allows for the cycle to be closed at temperatures below 1,000?°C. The production of hydrogen and oxygen is fully reproducible for at least five cycles. PMID:22647608

  5. CHROMIUM TRANSPORT, OXIDATION, AND ADSORPTION IN MANGANESE-COATED SAND

    EPA Science Inventory

    We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (P-MnO$-coated sand. We find that P-Mn02 effectively oxidizes Cr@I) to Cr(VI) and that the extent of oxida...

  6. Direct electrochemistry and electrocatalysis with horseradish peroxidase immobilized in polyquaternium-manganese oxide nanosheet nanocomposite films

    Microsoft Academic Search

    Xiushuang Yang; Xu Chen; Wensheng Yang; David G. Evans

    2008-01-01

    A novel biocompatible polyquaternium (QY)-manganese oxide nanosheet (MNS) nanocomposite has been prepared and shown to be a promising matrix for horseradish peroxidase (HRP) immobilization. The resulting HRP-QY-MNS film was characterized by Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopy, which indicated that HRP retained its native structure in the nanocomposite film. An HRP-QY-MNS film-modified glassy carbon electrode exhibited a

  7. Nanocomposites of manganese oxides and carbon nanotubes for aqueous supercapacitor stacks

    Microsoft Academic Search

    Shengwen Zhang; Chuang Peng; Kok C. Ng; George Z. Chen

    2010-01-01

    Symmetrical supercapacitors and their serially connected two-cell stacks via a bipolar electrode were constructed with nanocomposites of manganese oxides and carbon nanotubes (MnOx\\/CNTs) as the electrode materials. Nanocomposites with different contents of MnOx were synthesised through the redox reaction between KMnO4 and CNTs in aqueous solutions. The nanocomposites were characterised by scanning and transmission electron microscopy, BET nitrogen adsorption and

  8. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    USGS Publications Warehouse

    Harvey, J.W.; Fuller, C.C.

    1998-01-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheicflow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/??(s), of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/??(h) = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/?? = 2.7 hours). The modeled depths of subsurface storage zones (d(s) = 4-17 cm) and modeled residence times of water in storage zones (t(s) = 3-12 min) were both consistent with direct measurements in hyporheic flow paths (d(h) = 0-15 cm, and t(h) = 1-25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (f(s) = 8.9%, and f(h) = 9.3%). Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1??(s) ??? 1.3 hours), and the hyporheic porewater residence timescale (t(s) ??? 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (L(s) = stream velocity/storage-zone exchange coefficient ??? 1.3 km) and the length of Pinal Creek (L ??? 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, R(s) = ??(s)t(s)L/L(s) (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of R(s) > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

  9. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    NASA Astrophysics Data System (ADS)

    Harvey, Judson W.; Fuller, Christopher C.

    1998-04-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/?s, of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/?h = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/? = 2.7 hours). The modeled depths of subsurface storage zones (ds = 4-17 cm) and modeled residence times of water in storage zones (ts = 3-12 min) were both consistent with direct measurements in hyporheic flow paths (dh = 0-15 cm, th = 1-25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (fs = 8.9%, andfh = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1/?s ? 1.3 hours), and the hyporheic porewater residence timescale (ts ? 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (Ls = stream velocity/storage-zone exchange coefficient ? 1.3 km) and the length of Pinal Creek (L ? 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, Rs = ?stsL/Ls (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of Rs > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

  10. Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

    USGS Publications Warehouse

    Huebner, J.S.; Flohr, M.J.K.; Grossman, J.N.

    1992-01-01

    Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes. ?? 1992.

  11. Manganese-oxidizing photosynthesis before the rise of cyanobacteria

    PubMed Central

    Johnson, Jena E.; Webb, Samuel M.; Thomas, Katherine; Ono, Shuhei; Kirschvink, Joseph L.; Fischer, Woodward W.

    2013-01-01

    The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however, the processes that led to the evolution of biological water splitting have remained largely unknown. To illuminate this history, we examined the behavior of the ancient Mn cycle using newly obtained scientific drill cores through an early Paleoproterozoic succession (2.415 Ga) preserved in South Africa. These strata contain substantial Mn enrichments (up to ?17 wt %) well before those associated with the rise of oxygen such as the ?2.2 Ga Kalahari Mn deposit. Using microscale X-ray spectroscopic techniques coupled to optical and electron microscopy and carbon isotope ratios, we demonstrate that the Mn is hosted exclusively in carbonate mineral phases derived from reduction of Mn oxides during diagenesis of primary sediments. Additional observations of independent proxies for O2—multiple S isotopes (measured by isotope-ratio mass spectrometry and secondary ion mass spectrometry) and redox-sensitive detrital grains—reveal that the original Mn-oxide phases were not produced by reactions with O2, which points to a different high-potential oxidant. These results show that the oxidative branch of the Mn cycle predates the rise of oxygen, and provide strong support for the hypothesis that the water-oxidizing complex of photosystem II evolved from a former transitional photosystem capable of single-electron oxidation reactions of Mn. PMID:23798417

  12. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    PubMed Central

    Fenske, Daniela; Bardenhagen, Ingo; Westphal, Anne; Knipper, Martin; Plaggenborg, Thorsten; Kolny-Olesiak, Joanna; Parisi, Jürgen

    2015-01-01

    Summary Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx + oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous ?-Mn2O3 particles were synthesized by calcination of Mn(II) glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD) measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II) glycolate precursor to ?-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM) and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous ?-Mn2O3 species. PMID:25671151

  13. c-Type Cytochromes and Manganese Oxidation in Pseudomonas putida MnB1

    PubMed Central

    Caspi, Ron; Tebo, Bradley M.; Haygood, M. G.

    1998-01-01

    Pseudomonas putida MnB1 is an isolate from an Mn oxide-encrusted pipeline that can oxidize Mn(II) to Mn oxides. We used transposon mutagenesis to construct mutants of strain MnB1 that are unable to oxidize manganese, and we 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. PMID:9758766

  14. Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction.

    SciTech Connect

    Lee, Ji-Hoon; Kennedy, David W.; Dohnalkova, Alice; Moore, Dean A.; Nachimuthu, Ponnusamy; Reed, Samantha B.; Fredrickson, Jim K.

    2011-12-27

    The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced ?-MnS (rambergite) nanoparticles under the concurrent reduction of synthetic MnO2 and thiosulfate coupled to H2 oxidation. Using two MR-1 mutants defective in outer membrane c-type cytochromes (?mtrC/?omcA and ?mtrC/?omcA/?mtrF) to eliminate the direct reduction pathway for solid electron acceptors, it was determined that respiratory reduction of MnO2 was dominant relative to chemical reduction by biogenic sulfide generated from bacterial thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of MR-1 using lactate as the sole electron donor produced MnCO3 (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO3 formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions that favor the precipitation of MnS. Formation of the biogenic MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modeling predictions. Although biogenic MnS likely only forms and is stable over a relatively narrow range of conditions, it may be a significant sink for Mn in anoxic marine basins and terrestrial subsurface sediments where Mn and sulfur compounds are undergoing concurrent reduction.

  15. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  16. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M. (Hayward, CA); Peng, Marcus Y. (Cupertino, CA); Ma, Yanping (Albany, CA); Visco, Steven J. (Berkeley, CA); DeJonghe, Lutgard C. (Lafayette, CA)

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  17. Manganese Based Oxidative Technologies For Water/Wastewater Treatment

    E-print Network

    Desai, Ishan

    2013-08-27

    as different pH's. The reaction order was found to be ? 1.1 for both oxide as well as the organic. The reactivity was much higher under acidic conditions. The presence of metals and humic acids greatly reduced the reactivity. The primary reaction by...

  18. Microbial reduction of manganese oxides - Interactions with iron and sulfur

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

  19. Electrochromic performance, wettability and optical study of copper manganese oxide thin films: Effect of annealing temperature

    NASA Astrophysics Data System (ADS)

    Falahatgar, S. S.; Ghodsi, F. E.; Tepehan, F. Z.; Tepehan, G. G.; Turhan, ?.

    2014-01-01

    In the present work, the nanostructured copper manganese oxide (CMO) thin films were prepared from acetate based sol-gel precursors and deposited on glass and indium tin oxide (ITO) substrates by dip-coating technique. The films were annealed at 300, 400 and 500 °C in ambient atmosphere. The effects of annealing temperature on structural, morphological, wettability, electrochromic and optical properties of CMO thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDX), water contact angle measurement (WCA), cyclic voltammetry (CV) measurements and ultraviolet-visible (UV-vis) spectrophotometery. The presence of mixed oxide phases comprising of copper manganese oxide (CuMn2O4) and manganese oxide at different annealing temperature was confirmed by XRD patterns. The results showed that the Mn3O4 phase has been changed to Mn2O3 when the annealing temperature is increased from 300 to 500 °C. The FESEM images indicated that the granular surface morphology was sensitive to annealing temperature. EDX studies indicated that the thin films contained O, Mn and Cu species. Wettability studies showed that the water contact angle of the nanostructured CMO thin films coated on glass substrates was influenced by the variation of annealing temperature and the surface nature of thin films was changed from hydrophilic to hydrophobic. The results of CVs measurement indicated that the anodic and cathodic charge density and capacitance of all CMO samples decreased with increasing scan rate in potential range of -1-1 eV. Also, the annealed CMO thin film at 500 °C showed better electrochromic performance with respect to other samples at lower scan rate. The thickness, refractive index, extinction coefficient and optical band gap of thin films coated on glass substrates were calculated from reflectance and transmittance spectra using an iterative numerical method. The optical band gap of nanostructured CMO thin films increased with increasing annealing temperature.

  20. Airborne manganese exposure differentially affects end points of oxidative stress in an age-and sex-dependent manner

    Microsoft Academic Search

    Keith M. Erikson; David C. Dorman; Lawrence H. Lash; Allison W. Dobson; Michael Aschner

    2004-01-01

    Juvenile female and male (young) and 16-mo-old male (old) rats inhaled manganese in the form of manganese sulfate (MnSO4) at 0, 0.01, 0.1, and 0.5 mg Mn\\/m3 or manganese phosphate at 0.1 mg Mn\\/m3 in exposures of 6h\\/d, 5d\\/wk for 13 wk. We assessed biochemical end points indicative of oxidative stress in five brain regions:\\u000a cerebellum, hippocampus, hypothalamus, olfactory bulb,

  1. Part I. Manganese oxide containing layered double hydroxides materials: Synthesis and characterization. Part II. Manganese oxide octahedral molecular sieves (OMS-2): Synthesis, particle size control, characterization, and catalytic applications

    NASA Astrophysics Data System (ADS)

    Villegas, Josanlet C.

    The work presented here comprises the development of new routes for the preparation of manganese oxide-based materials with controlled properties. The first part of the research consists of the preparation of a new series of layered double hydroxide (LDH) materials containing intercalated manganese oxide species. Characterization of the resulting materials will be sub-divided in two major parts: (1) Composition, structural, and textural properties and (2) Determination of the oxidation state of the manganese species formed. The process of incorporating manganese oxides into the LDH materials takes place by a simple two-step method which involves the ion-exchange of nitrate anions with high valence manganese precursor anions followed by the in-situ reaction between the manganese anions and organic reducing agents. The method developed allows the preparation of a wide range of Mn-intercalated LDHs by simply changing the reducing agent used. In the second part of the research a new "soft" chemistry method to prepare manganese oxide octahedral molecular sieves (OMS-2) materials with controlled crystalline particle sizes will be presented. The synthesis is based on the use of H2O2 to reduce MnO4- under acidic conditions. The particle size is controlled by the concentration of H2O2 in the reaction media. The structural and textural properties of the synthesized OMS-2 are investigated. The catalytic activity and structural properties of these OMS-2 nanomaterials for oxidation catalysis will also be discussed. The work will continue with the investigation on the framework substitution of higher valency transition metal ions (TM = Nb, V) into the OMS-2 materials. The incorporation of TM into the structure of OMS-2 occurs by reacting the manganese and TM source with an oxidant under hydrothermal conditions. The structural properties, oxidation state of manganese, TM loading, and location of the TM in the OMS-2 structure will be investigated. The versatility of OMS-2 to accommodate higher valence TM metals is demonstrated. The last part of the research comprises the study of the electrical resistivity of OMS-2 materials. The effect of the different OMS-2 synthesis method and the framework doping is investigated. A correlation of the resistivities of all the OMS materials prepared in our laboratory and their structures is presented.

  2. Effects of solar radiation on manganese oxide reactions with selected organic compounds

    SciTech Connect

    Bertino, D.J.; Zepp, R.G. (Environmental Protection Agency, Athens, GA (United States))

    1991-07-01

    The effects of sunlight on aqueous redox reactions between manganese oxides (MnO{sub x}) and selected organic substances are reported. No sunlight-induced rate enhancement was observed for the MnO{sub x} oxidation of substituted phenols, anisole, o-dichlorobenzene, or p-chloroaniline. On the other hand, solar radiation did accelerate the reduction of manganese oxides by dissolved organic matter (DOM) from aquatic environments. The photoreduction of MnO{sub x} by DOM was little affected by molecular oxygen in air-saturated water (250 {mu}M), but was inhibited by 2,6-dichloroindophenol (0.5-6 {mu}M), and excellent electron acceptor. MnO{sub x} reduction also was photosensitized by anthraquinone-2-sulfonate. These results indicate that the photoreduction probably involves electron transfer from excited states of sorbed DOM to the oxide surface. Wavelength studies indicated that ultraviolet-B radiation (280-320 nm) plays an important role in this photoreduction.

  3. Influence of extractable soil manganese on oxidation capacity of different soils in Korea

    NASA Astrophysics Data System (ADS)

    Chon, Chul-Min; Kim, Jae Gon; Lee, Gyoo Ho; Kim, Tack Hyun

    2008-08-01

    We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00-0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mnd), NH2OH·HCl (Mnh), and hydroquinone (Mnr) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH2OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH2OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mnd, Mnh, and Mnr showed a relatively high correlation with the Cr tests ( r = 0.655-0.851; P < 0.01). The concentrations of Mnd and Mnh were better correlated with the Cr oxidation tests than was the Mnr concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mnd and Mnh than by Mnr. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).

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

    NASA Astrophysics Data System (ADS)

    Pena, J.; Sposito, G.

    2009-12-01

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

  5. Manganese(II)-Oxidizing Bacillus Spores in Guaymas Basin Hydrothermal Sediments and Plumes

    PubMed Central

    Dick, Gregory J.; Lee, Yifan E.; Tebo, Bradley M.

    2006-01-01

    Microbial oxidation and precipitation of manganese at deep-sea hydrothermal vents are important oceanic biogeochemical processes, yet nothing is known about the types of microorganisms or mechanisms involved. Here we report isolation of a number of diverse spore-forming Mn(II)-oxidizing Bacillus species from Guaymas Basin, a deep-sea hydrothermal vent environment in the Gulf of California, where rapid microbially mediated Mn(II) oxidation was previously observed. mnxG multicopper oxidase genes involved in Mn(II) oxidation were amplified from all Mn(II)-oxidizing Bacillus spores isolated, suggesting that a copper-mediated mechanism of Mn(II) oxidation could be important at deep-sea hydrothermal vents. Phylogenetic analysis of 16S rRNA and mnxG genes revealed that while many of the deep-sea Mn(II)-oxidizing Bacillus species are very closely related to previously recognized isolates from coastal sediments, other organisms represent novel strains and clusters. The growth and Mn(II) oxidation properties of these Bacillus species suggest that in hydrothermal sediments they are likely present as spores that are active in oxidizing Mn(II) as it emerges from the seafloor. PMID:16672456

  6. Coprecipitation and redox reactions of manganese oxides with copper and nickel

    USGS Publications Warehouse

    Hem, J.D.; Lind, C.J.; Roberson, C.E.

    1989-01-01

    Open-system, continuous-titration experiments have been done in which a slow flux of ???0.02 molar solution of Mn2+ chloride, nitrate, or perchlorate with Cu2+ or Ni2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu2Mn3O8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, ??MnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included ??MnOOH, Ni(OH)2, and the same two forms of MnO2. The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu2+ and Ni2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems. ?? 1989.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  8. Metalloradical Complexes of Manganese and Chromium Featuring an Oxidatively Rearranged Ligand

    PubMed Central

    Çelenligil-Çetin, Remle; Paraskevopoulou, Patrina; Lalioti, Nikolia; Sanakis, Yiannis; Staples, Richard J.; Rath, Nigam P.; Stavropoulos, Pericles

    2009-01-01

    Redox events involving both metal and ligand sites are receiving increased attention since a number of biological processes direct redox equivalents toward functional residues. Metalloradical synthetic analogs remain scarce and require better definition of their mode of formation and subsequent operation. The trisamido-amine ligand [(RNC6H4)3N]3?, where R is the electron-rich 4-t-BuPh, is employed in this study to generate redox active residues in manganese and chromium complexes. Solutions of [(L1)Mn(II)–THF]? in THF are oxidized by dioxygen to afford [(L1re–1)Mn(III)–(O)2–Mn(III)(L1re–1)]2? as the major product. The rare dinuclear manganese (III,III) core is stabilized by a rearranged ligand that has undergone an one-electron oxidative transformation, followed by retention of the oxidation equivalent as a ? radical in an o-diiminobenzosemiquinonate moiety. Magnetic studies indicate that the ligand-centered radical is stabilized by means of extended antiferromagnetic coupling between the S = ½ radical and the adjacent S = 2 Mn(III) site, as well as between the two Mn(III) centers via the dioxo bridge. Electrochemical and EPR data suggest that this system can store higher levels of oxidation potency. Entry to the corresponding Cr(III) chemistry is achieved by employing CrCl3 to access both [(L1)Cr(III)–THF] and [(L1re–1)Cr(III)–THF(Cl)], featuring the intact and the oxidatively rearranged ligands, respectively. The latter is generated by ligand-centered oxidation of the former compound. The rearranged ligand is perceived to be the product of an one-electron oxidation of the intact ligand to afford a metal-bound aminyl radical that subsequently mediates a radical 1,4-(N-to-N) aryl migration. PMID:18937446

  9. Geology, alteration, age, and origin of iron oxide-apatite deposits in Upper Eocene quartz monzonite, Zanjan district, NW Iran

    NASA Astrophysics Data System (ADS)

    Nabatian, Ghasem; Ghaderi, Majid; Corfu, Fernando; Neubauer, Franz; Bernroider, Manfred; Prokofiev, Vsevolod; Honarmand, Maryam

    2014-02-01

    Iron oxide-apatite deposits are present in Upper Eocene pyroxene-quartz monzonitic rocks of the Zanjan district, northwestern Iran. Mineralization occurred in five stages: (1) deposition of disseminated magnetite and apatite in the host rock; (2) mineralization of massive and banded magnetite ores in veins and stockwork associated with minor brecciation and calcic alteration of host rocks; (3) deposition of sulfide ores together with potassic alteration; (4) formation of quartz and carbonate veins and sericite, chlorite, epidote, silica, carbonate, and tourmaline alteration; and (5) supergene alteration and weathering. U-Pb dating of monazite inclusions in the apatite indicates an age of 39.99 ± 0.24 Ma, which is nearly coeval with the time of emplacement of the host quartz monzonite, supporting the genetic connection. Fluid inclusions in the apatite have homogenization temperatures of about 300 °C and oxygen isotopic compositions of the magnetite support precipitation from magmatic fluids. Late-stage quartz resulted from the introduction of a cooler, less saline, and isotopically depleted fluid. The iron oxide-apatite deposits in the Tarom area of the Zanjan district are typical of a magmatic-hydrothermal origin and are similar to the Kiruna-type deposits with respect to mineral assemblages, fabric and structure of the iron ores, occurrence of the ore bodies, and wall rock alteration.

  10. Defect Physics, Delithiation Mechanism, and Electronic and Ionic Conduction in Layered Lithium Manganese Oxide Cathode Materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang

    2015-02-01

    Layered Li Mn O2 and Li2Mn O3 are of great interest for lithium-ion battery cathodes because of their high theoretical capacities. The practical application of these materials is, however, limited due to poor electrochemical performance. We herein report a comprehensive first-principles study of defect physics in Li Mn O2 and Li2Mn O3 using hybrid density-functional calculations. We find that manganese antisites have low formation energies in Li Mn O2 and may act as nucleation sites for the formation of impurity phases. The antisites can also occur with high concentrations in Li2Mn O3 ; however, unlike in Li Mn O2 , they can be eliminated by tuning the experimental conditions during preparation. Other intrinsic point defects may also occur and have an impact on the materials' properties and functioning. An analysis of the formation of lithium vacancies indicates that lithium extraction from Li Mn O2 is associated with oxidation at the manganese site, resulting in the formation of manganese small hole polarons; whereas in Li2Mn O3 the intrinsic delithiation mechanism involves oxidation at the oxygen site, leading to the formation of bound oxygen hole polarons ?O+ . The layered oxides are found to have no or negligible bandlike carriers, and they cannot be doped n or p type. The electronic conduction proceeds through hopping of hole and/or electron polarons; the ionic conduction occurs through lithium monovacancy and/or divacancy migration mechanisms. Since ?O+ is not stable in the absence of negatively charged lithium vacancies in bulk Li2Mn O3 , the electronic conduction near the start of delithiation is likely to be poor. We suggest that the electronic conduction associated with ?O+ and, hence, the electrochemical performance of Li2Mn O3 can be improved through nanostructuring and/or ion substitution.

  11. Study of quartz crystal microbalance NO2 sensor coated with sputtered indium tin oxide film

    NASA Astrophysics Data System (ADS)

    Georgieva, V.; Aleksandrova, M.; Stefanov, P.; Grechnikov, A.; Gadjanova, V.; Dilova, T.; Angelov, Ts

    2014-12-01

    A study of NO2 gas sorption ability of thin indium tin oxide (ITO) deposited on 16 MHz quartz crystal microbalance (QCM) is presented. ITO films are grown by RF sputtering of indium/tin target with weight proportion 95:5 in oxygen environment. The ITO films have been characterized by X-ray photoelectron spectroscopy measurements. The ITO surface composition in atomic % is defined to be: In-40.6%, Sn-4.3% and O-55%. The thickness and refractive index of the films are determined by ellipsometric method. The frequency shift of QCM-ITO is measured at different NO2 concentrations. The QCM-ITO system becomes sensitive at NO2 concentration >= 500 ppm. The sorbed mass for each concentration is calculated according the Sauerbrey equation. The results indicated that the 1.09 ng of the gas is sorbed into 150 nm thick ITO film at 500 ppm NO2 concentration. When the NO2 concentration increases 10 times the calculated loaded mass is 5.46 ng. The sorption process of the gas molecules is defined as reversible. The velocity of sorbtion /desorption processes are studied, too. The QCM coated with thin ITO films can be successfully used as gas sensors for detecting NO2 in the air at room temperature.

  12. Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes

    PubMed Central

    Young, Karin J.; Gao, Yunlong; Brudvig, Gary W.

    2011-01-01

    Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [Mn4IVO5(terpy)4(H2O)2](ClO4)6 (terpy = 2,2?;6?,2?-terpyridine), [Mn4O6(tacn)4](ClO4)4 (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide conducting glass electrodes. The electrodes are illuminated with white light in the presence of an applied potential and the resulting photocurrent is assigned to the oxidation of solvent water. Photodecomposition of the tetrameric complexes results in a material that is more active for light-driven electrooxidation of water. The reactivity, wavelength dependence, and stability of the compounds in Nafion under illumination are discussed. PMID:22140273

  13. Pathogenic prion protein is degraded by a manganese oxide mineral found in soils

    USGS Publications Warehouse

    Russo, F.; Johnson, C.J.; McKenzie, D.; Aiken, J.M.; Pedersen, J.A.

    2009-01-01

    Prions, the aetiological agents of transmissible spongiform encephalopathies, exhibit extreme resistance to degradation. Soil can retain prion infectivity in the environment for years. Reactive soil components may, however, contribute to the inactivation of prions in soil. Members of the birnessite family of manganese oxides (MnO2) rank among the strongest natural oxidants in soils. Here, we report the abiotic degradation of pathogenic prion protein (PrPTSE) by a synthetic analogue of naturally occurring birnessite minerals. Aqueous MnO2 suspensions degraded the PrPTSE as evidenced by decreased immunoreactivity and diminished ability to seed protein misfolding cyclic amplification reactions. Birnessite-mediated PrPTSE degradation increased as a solution's pH decreased, consistent with the pH-dependence of the redox potential of MnO2. Exposure to 5.6 mg MnO2 ml-1 (PrPTSE:MnO2=1 : 110) decreased PrPTSE levels by ???4 orders of magnitude. Manganese oxides may contribute to prion degradation in soil environments rich in these minerals. ?? 2009 SGM.

  14. Electronic and magnetic structure of LaSr-2×4 manganese oxide molecular sieve nanowires.

    PubMed

    Gazquez, Jaume; Carretero-Genevrier, Adrián; Gich, Martí; Mestres, Narcís; Varela, María

    2014-06-01

    In this study we combine scanning transmission electron microscopy, electron energy loss spectroscopy and electron magnetic circular dichroism to get new insights into the electronic and magnetic structure of LaSr-2×4 manganese oxide molecular sieve nanowires integrated on a silicon substrate. These nanowires exhibit ferromagnetism with strongly enhanced Curie temperature (T c >500 K), and we show that the new crystallographic structure of these LaSr-2×4 nanowires involves spin orbital coupling and a mixed-valence Mn3+/Mn4+, which is a must for ferromagnetic ordering to appear, in line with the standard double exchange explanation. PMID:24735528

  15. Nanostructured and layered lithium manganese oxide and method of manufacturing the same

    NASA Technical Reports Server (NTRS)

    Singhal, Amit (Inventor); Skandan, Ganesh (Inventor)

    2005-01-01

    Nanostructured and layered lithium manganese oxide powders and methods of producing same. The powders are represented by the chemical formula, LixMn1-yMyO2, where 0.5

  16. The simple preparation of birnessite-type manganese oxide with flower-like microsphere morphology and its remarkable capacity retention

    SciTech Connect

    Zhu, Gang; Deng, Lingjuan; Wang, Jianfang; Kang, Liping [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China) [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China); School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China); Liu, Zong-Huai, E-mail: zhliu@snnu.edu.cn [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China) [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China); School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China)

    2012-11-15

    Graphical abstract: Flower-like birnessite-type manganese oxide microspheres with large specific surface area and excellent electrochemical properties have been prepared by a facile hydrothermal method. Highlights: ? Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area. ? A facile low-temperature hydrothermal method. ? Novel flower-like microsphere consists of the thin nano-platelets. ? Birnessite-type manganese oxide exhibits an ideal capacitive behavior and excellent cycling stability. -- Abstract: Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area has been prepared by hydrothermal treating a mixture solution of KMnO{sub 4} and (NH{sub 4}){sub 2}SO{sub 4} at 90 °C for 24 h. The obtained material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N{sub 2} adsorption–desorption. Results indicate that the birnessite-type manganese oxide shows novel flower-like microsphere morphology and a specific surface area of 280 m{sup 2} g{sup ?1}, and the flower-like microsphere consists of the thin nano-platelets. Electrochemical characterization indicates that the prepared material exhibits an ideal capacitive behavior with a capacitance value of 278 F g{sup ?1} in 1 mol L{sup ?1} Na{sub 2}SO{sub 4} aqueous solution at a scan rate of 5 mV s{sup ?1}. Moreover, the prepared manganese oxide electrode shows excellent cycle stability, and the specific capacitance can maintain 98.6% of the initial one after 5000 cycles.

  17. Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

    SciTech Connect

    Gallegos, María V., E-mail: plapimu@yahoo.com.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Falco, Lorena R., E-mail: mlfalco@quimica.unlp.edu.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Peluso, Miguel A., E-mail: apelu@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Sambeth, Jorge E., E-mail: sambeth@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Thomas, Horacio J. [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina)

    2013-06-15

    Highlights: • Manganese oxides were synthesized using spent batteries as raw materials. • Spent alkaline and zinc–carbon size AA batteries were used. • A biohydrometallurgical process was employed to bio-lixiviate batteries. • Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  18. Behaviour of a fluorine-doped tin oxide electrode: a study by quartz crystal microbalance in propylene carbonate

    Microsoft Academic Search

    M. Székely; C. Mathieu; N. E. Moulayat; M. Herlem; H. Cachet; M. Keddam; H. Perrot; B. Fahys; B. Eid; E. Caillot

    1996-01-01

    Fluorine-doped tin oxide (FTO) was deposited onto a gold electrode evaporated onto a quartz crystal. The FTO material was cycled in propylene carbonate in the presence of 1 M LiClO4. Voltammetric and gravimetric responses of the FTO electrode were recorded between +2.75 and +0.75 V vs. Li|Li+ for 180 cycles. During the first few cycles, reduction of trace water was

  19. Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts.

    PubMed

    Liang, Yongye; Wang, Hailiang; Zhou, Jigang; Li, Yanguang; Wang, Jian; Regier, Tom; Dai, Hongjie

    2012-02-22

    Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co(3)O(4) nanoparticles, a manganese-cobalt spinel MnCo(2)O(4)/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near-edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrids results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C-O and C-N bonding in the N-rmGO sheet, suggesting the formation of C-O-metal and C-N-metal bonds between N-doped graphene oxide and spinel oxide nanoparticles. Co L-edge and Mn L-edge XANES suggested substitution of Co(3+) sites by Mn(3+), which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared with the pure cobalt oxide hybrid. The covalently bonded hybrid afforded much greater activity and durability than the physical mixture of nanoparticles and carbon materials including N-rmGO. At the same mass loading, the MnCo(2)O(4)/N-graphene hybrid can outperform Pt/C in ORR current density at medium overpotentials with stability superior to Pt/C in alkaline solutions. PMID:22280461

  20. Sodium manganese oxide thin films as cathodes for Na-ion batteries

    SciTech Connect

    Baggetto, Loic [ORNL; Carroll, Kyler J [University of California, San Diego; Unocic, Raymond R [ORNL; Bridges, Craig A [ORNL; Meng, Ying Shirley [University of California, San Diego; Veith, Gabriel M [ORNL

    2014-01-01

    This paper presents the fabrication and characterization of sodium manganese oxide cathode thin films for rechargeable Na-ion batteries. Layered oxide compounds of nominal compositions Na0.6MnO2 and Na1.0MnO2 have been prepared by radio frequency magnetron sputtering and post-annealing at high temperatures under various conditions. The Na0.6MnO2 thin films possess either a hexagonal or orthorhombic structure while the Na1.0MnO2 films crystallize in a monoclinic structure, as shown by X-ray diffraction and X-ray absorption spectroscopy results. The potential profiles of the film cathodes are characterized by features similar to those measured for the powders and exhibit reversible storage capacities in the range of 50-60 Ah cm-2 m-1, which correspond to about 120-140 mAh g-1, and are maintained over 80 cycles.

  1. Electrochemical impedance spectroscopy studies of lithium diffusion in doped manganese oxide

    SciTech Connect

    Johnson, B.J.; Doughty, D.H.; Voigt, J.A.; Boyle, T.J.

    1996-06-01

    Cathode performance is critical to lithium ion rechargeable battery performance; effects of doping lithium manganese oxide cathode materials on cathode performance are being investigated. In this paper, Li diffusion in Al-doped LiMn{sub 2}O{sub 4} was studied and found to be controlled by the quantity of Al dopant. Electrochemical cycling was conducted at 0.5mA/cm{sub 2}; electrochemical impedance spectra were taken at open circuit potential, with impedance being measured at 65 kHz-0.01 Hz. As the Al dopant level was increased, the Li diffusion rate decreased; this was attributed to the decreased lattice parameter of the doped oxide.

  2. Adsorption of copper, cadmium, lead and zinc onto a synthetic manganese oxide.

    PubMed

    Della Puppa, Loïc; Komárek, Michael; Bordas, François; Bollinger, Jean-Claude; Joussein, Emmanuel

    2013-06-01

    Due to its simple and inexpensive synthesis, a new amorphous hydrous manganese oxide (AMO) has been studied as a possible chemical stabilizing agent for soils contaminated with metals. Preliminary experiments evaluating the stability of AMO in pure water have reported only minor dissolution (5.70% and 0.24% depending on the w/v ratio). Sorption kinetics have shown fast metal adsorption, especially for Pb. The sorption capacities of AMO for Cu, Cd, Pb, and Zn have been described and compared with synthetic birnessite for pH 4 and 5.5. Both oxides show similar sorption capacities at pH 4 despite the fact that birnessite characteristics (pH of zero point charge, specific surface area and cation exchange capacity) are more favorable for metal sorption. Moreover, the pH adsorption-edges show that the AMO is more pH-dependent than birnessite. PMID:23566588

  3. In Situ X-ray Absorption Study of a Layered Manganese-chromium Oxide-based Cathode Material

    SciTech Connect

    Balasubramanian, M.; McBreen, J; Davidson, I; Whitfield, P; Kargina, I

    2010-01-01

    We have investigated the electronic and atomic structure of a manganese-chromium-based layered oxide material Li[Li{sub 0.2}Cr{sub 0.4}Mn{sub 0.4}]O{sub 2} during electrochemical cycling using in situ X-ray absorption spectroscopy. Our results indicate that charge compensation in the cathode material is achieved by the oxidation/reduction of octahedral Cr(III) ions to tetrahedral Cr(VI) ions during delithiation/lithiation. Manganese ions are present predominantly in the Mn(IV) oxidation state and do not appear to actively participate in the charge compensation process. To accommodate the large changes in coordination symmetry of the Cr(III) and Cr(VI) ions, the chromium ions have to move between the regular octahedral sites in the R{bar 3}m-like lattice to interstitial tetrahedral sites during the charge/discharge process. The highly reversible (at least after the first charge) three-electron oxidation/reductions and the easy mobility of the chromium between octahedral and tetrahedral sites are very unusual and interesting. Equally interesting is the fact that chromium is the active metal undergoing oxidation/reduction rather than manganese. Our results also suggest that in the local scale manganese and chromium ions are not evenly distributed in the as-prepared material, but are present in separate domains of Mn and Cr-rich regions.

  4. Applications of manganese oxides based catalyst for the destruction of VOCs

    SciTech Connect

    Singh, N.; Pisarczyk, K.S.; Sigmund, J.J. [Carus Chemical Co., LaSalle, IL (United States)

    1997-12-31

    Catalytic oxidation, as a proven control technology, has demonstrated a high level of efficiency in reducing Volatile Organic Compound (VOC`s) at competitive, and in many cases, lower cost than the other thermal incineration methods. Catalytic oxidation is the preferred technology for the destruction of VOC`s in a variety of industries; such as, flexographic printing, metal can coating, contract sterilization and bakeries. A key component of these catalytic systems is the catalyst itself, and transition metal oxide catalysts have demonstrated their advantage and overall superior applicability in numerous installations. The higher VOC destruction efficiencies of these catalysts, particularly for oxygenated VOC`s, allows for a lower temperature of operation making these catalysts an economically attractive alternative based upon the energy savings when compared to noble metal catalysts. Manganese based oxide catalysts are available in either homogenous extruded form or in monolith form, depending upon their application. The performance characteristics - measured as VOC destruction efficiencies - of these catalysts are dependent upon the operating conditions of the catalytic reactor. Reactor configuration and operating conditions; such as, catalyst operating temperature, gas phase linear velocity, contact time of the gas stream with the catalyst, and finally the characteristics of the hydrocarbon, all influence the efficiency of these catalytic systems. Models relating the hydrocarbon destruction efficiencies of these catalysts, as it is affected by these parameters, will be presented. These parametric models allow for comparison of various alternative catalyst strategies to be applied to a VOC destruction situation in the design phase. Data will be presented on a transition metal extruded catalyst, an extended temperature range manganese based catalyst, as well as a monolithic form of the transition metal catalyst.

  5. Influence of calcium(II) and chloride on the oxidative reactivity of a manganese(II) complex of a cross-bridged cyclen ligand.

    PubMed

    Zhang, Zhan; Coats, Katherine L; Chen, Zhuqi; Hubin, Timothy J; Yin, Guochuan

    2014-11-17

    Available data from different laboratories have confirmed that both Ca(2+) and Cl(-) are crucial for water oxidation in Photosystem II. However, their roles are still elusive. Using a manganese(II) complex having a cross-bridged cyclen ligand as a model, the influence of Ca(2+) on the oxidative reactivity of the manganese(II) complex and its corresponding manganese(IV) analogue were investigated. It has been found that adding Ca(2+) can significantly improve the oxygenation efficiency of the manganese(II) complex in sulfide oxidation and further accelerate the oxidation of sulfoxide to sulfone. Similar improvements have also been observed for Mg(2+), Sr(2+), and Ba(2+). A new monomeric manganese(IV) complex having two cis-hydroxide ligands has also been isolated through oxidation of the corresponding manganese(II) complex with H2O2 in the presence of NH4PF6. This rare cis-dihydroxomanganese(IV) species has been well characterized by X-ray crystallography, electrochemistry, electron paramagnetic resonance, and UV-vis spectroscopy. Notably, using the manganese(IV) complex as a catalyst demonstrates higher activity than the corresponding manganese(II) complex, and adding Ca(2+) further improves its catalytic efficiency. However, adding Cl(-) decreases its catalytic activity. In electrochemical studies of manganese(IV) complexes with no chloride ligand present, adding Ca(2+) positively shifted the redox potential of the Mn(IV)/Mn(III) couple but negatively shifted its Mn(V)/Mn(IV) couple. In the manganese(II) complex having a chloride ligand, adding Ca(2+) shifted both the Mn(IV)/Mn(III) and Mn(V)/Mn(IV) couples in the negative direction. The revealed oxidative reactivity and redox properties of the manganese species affected by Ca(2+) and Cl(-) may provide new clues to understanding their roles in the water oxidation process of Photosystem II. PMID:25375413

  6. Manganese-oxide minerals in fractures of the Crater Flat Tuff in drill core USW G-4, Yucca Mountain, Nevada

    SciTech Connect

    Carlos, B.A.; Bish, D.L.; Chipera, S.J.

    1990-07-01

    The Crater Flat Tuff is almost entirely below the water table in drill hole USW G-4 at Yucca Mountain, Nevada. Manganese-oxide minerals from the Crater Flat Tuff in USW G-4 were studied using optical, scanning electron microscopic, electron microprobe, and x-ray powder diffraction methods to determine their distribution, mineralogy, and chemistry. Manganese-oxide minerals coat fractures in all three members of the Crater Flat Tuff (Prow Pass, Bullfrog, and Tram), but they are most abundant in fractures in the densely welded devitrified intervals of these members. The coatings are mostly of the cryptomelane/hollandite mineral group, but the chemistry of these coatings varies considerably. Some of the chemical variations, particularly the presence of calcium, sodium, and strontium, can be explained by admixture with todorokite, seen in some x-ray powder diffraction patterns. Other chemical variations, particularly between Ba and Pb, demonstrate that considerable substitution of Pb for Ba occurs in hollandite. Manganese-oxide coatings are common in the 10-m interval that produced 75% of the water pumped from USW G-4 in a flow survey in 1983. Their presence in water-producing zones suggests that manganese oxides may exert a significant chemical effect on groundwater beneath Yucca Mountain. In particular, the ability of the manganese oxides found at Yucca Mountain to be easily reduced suggests that they may affect the redox conditions of the groundwater and may oxidize dissolved or suspended species. Although the Mn oxides at Yucca Mountain have low exchange capacities, these minerals may retard the migration of some radionuclides, particularly the actinides, through scavenging and coprecipitation. 23 refs., 21 figs., 2 tabs.

  7. Manganese oxide-coated redox bars as an indicator for reducing soil conditions

    NASA Astrophysics Data System (ADS)

    Dorau, Kristof; Mansfeldt, Tim

    2014-05-01

    Field identification of reducing soil conditions is of concern not only for soil pedogenesis but also for nutrient and pollutant dynamics in soils. We manufactured manganese (Mn) oxide-coated polyvinyl chloride (PVC) bars and proved their suitability for identification of reducing soil conditions in both the laboratory and field. Birnessite (?-MnO2) was synthesized according to a recently published method and was coated onto white PVC bars. We used microcosm devices with adjusted redox potentials (EH) to distinguish the onset and intensity of depletion patterns along the Mn oxide-coating and soil column experiments combined with field application to validate the enhanced removal of Mn against Fe oxide-coated bars under anaerobe soil conditions. Field application was performed at a site with shallow and strongly fluctuating water tables where water table depth and soil temperature were monitored. Three microcosm experiments adjusted to oxidizing (EH ~500 mV, pH 7), weakly reducing (EH ~175 mV, pH 7) and moderately reducing conditions (EH ~25 mV, pH 7) showed depending on the EH no, slight, or intense removal of the Mn oxide-coating, respectively. Moreover, the removal of Mn oxide (225 mm2 d-1) in soil column experiments exceeded the removal of Fe oxide (118 mm2 d-1). The enhanced removal of the Mn oxide-coating was also found under anaerobe conditions in field application. Consequently, identifying of reducing conditions in soils by Mn oxide-coated bars is possible. We recommend using this methodology for short-term monitoring, e.g. on weekly basis, since tri- and tetravalent Mn is the preferred electron acceptor compared with trivalent Fe.

  8. Preparation of anionic clay-birnessite manganese oxide composites by interlayer oxidation of oxalate ions by permanganate

    SciTech Connect

    Arulraj, James [Materials Research Group, Department of Chemistry, St. Joseph's College, 36 Langford Road, Bangalore 560 027 (India)] [Materials Research Group, Department of Chemistry, St. Joseph's College, 36 Langford Road, Bangalore 560 027 (India); Rajamathi, Michael, E-mail: mikerajamathi@rediffmail.com [Materials Research Group, Department of Chemistry, St. Joseph's College, 36 Langford Road, Bangalore 560 027 (India)] [Materials Research Group, Department of Chemistry, St. Joseph's College, 36 Langford Road, Bangalore 560 027 (India)

    2013-02-15

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni{sub 3}Zn{sub 2}(OH){sub 8}(OAc){sub 2}{center_dot}2H{sub 2}O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used. - Graphical abstract: Nickel zinc hydroxyoxalate was reacted with potassium permanganate to get nickel zinc hydroxide birnessite composites in which the positive charges on the hydroxide layers are neutralized by the negative charges on birnessite layers. Highlights: Black-Right-Pointing-Pointer Anionic and cationic layered solid composites prepared. Black-Right-Pointing-Pointer Ni-Zn hydroxyoxalate reacted with KMnO{sub 4} to deposit MnO{sub 2} in the interlayer. Black-Right-Pointing-Pointer Birnessite layers coexist with anionic clay layers in the composites. Black-Right-Pointing-Pointer Birnessite/anionic clay ratio controlled by amount of KMnO{sub 4} used and reaction time.

  9. Molecular-Level Processes Governing the Interaction of Contaminants with Iron and Manganese Oxides - Final Report

    SciTech Connect

    Brown Jr., G. E.; Chambers, S. A.

    1999-10-31

    Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on structurally and compositionally well-defined mineral surfaces will lead to: (i) improved models of contaminant fate and transport in geochemical systems, and (ii) optimized manipulation of these processes for remediation purposes. To contribute to this understanding, we will study, both experimentally and theoretically, redox processes involving three important contaminants - chromate ion, carbon tetrachloride, and trichloroethene TCE, on the following iron and manganese oxides - hematite, magnetite, maghemite, and pyrolusite. These oxides and their hydroxylated analogs commonly occur as coatings on minerals or as interfaces in the subsurface environment. Single-crystal surfaces of these oxides will be synthesized in carefully controlled fashion by molecular beam epitaxy. These surfaces, as well as high surface are powdered samples of these oxides, will be used in spectroscopic and kinetic experiments in both aqueous and gas phases. Our goal is to identify products and to determine the kinetics and mechanisms of surface-catalyzed redox reaction of Cr(VI) and CR(III), and the reductive dechlorination of carbon tetrachloride and TCE. The combination of theory and experiment will provide the base information needed to scale from the molecular level to the microscopic grain level minerals.

  10. Stability of manganese-oxide-modified lanthanum strontium cobaltite in the presence of chromia

    NASA Astrophysics Data System (ADS)

    Ou, Ding Rong; Cheng, Mojie

    2014-12-01

    In order to restrain the decomposition and conductivity degradation of perovskite-type conductive material in the presence of chromia, manganese oxide modification of lanthanum strontium cobaltite has been studied. La0.7Sr0.3CoO3-? (LSC) and MnO2-modified LSC coatings are applied onto Ni-Cr alloy and exposed to long-term oxidation text to examine their chemical stability. In a LSC coating, chromium species migrating from the Ni-Cr alloy could induce the decomposition of LSC and produce SrCrO4 and Co-Cr spinel oxides. In contrast, in the MnO2-modified LSC, Sr is stable and the low-conductivity phase SrCrO4 phase is rarely seen even the coated alloy has gone through 1000 h of oxidation tests at 800 °C. It highlights that MnO2 modification could greatly improve the stability of LSC under Cr-rich conditions. The study of solid state reactions reveals that the influence of MnO2 is mainly due to the reaction between MnO2 and LSC, instead of the direct reaction between MnO2 and chromium oxides.

  11. Nanometer-sized manganese oxide-quenched fluorescent oligonucleotides: an effective sensing platform for probing biomolecular interactions.

    PubMed

    He, Dinggeng; He, Xiaoxiao; Wang, Kemin; Yang, Xue; Yang, Xiaoxiao; Li, Xuecai; Zou, Zhen

    2014-09-28

    We propose a novel template-assisted strategy to prepare nanometer-sized manganese oxide (nano-MnO2) by self-assembly of some MnO2 platelets and demonstrate its application as a new class of biosensing platform for probing DNA hybridization and aptamer-target interaction in a homogeneous solution. PMID:25098407

  12. ADSORPTION OF LEAD FROM A CONTAMINATED SOIL TREATED WITH PHOSPHORUS AND MANGANESE OXIDES BY APRAGUE-DAWLEY RATS

    EPA Science Inventory

    In addition to the formation of insoluble lead (Pb) compounds as a mean of reducing Pb bioavalability, adsorption is another potentially important process controlling the bioavailability of Pb in soils. Less attention has been given to manganese (Mn) oxides, even though they are ...

  13. Mesostructured amorphous manganese oxides: facile synthesis and highly durable elimination of low-concentration NO at room temperature in air.

    PubMed

    Du, Yanyan; Hua, Zile; Huang, Weimin; Wu, Meiying; Wang, Min; Wang, Jin; Cui, Xiangzhi; Zhang, Lingxia; Chen, Hangrong; Shi, Jianlin

    2015-04-01

    At a high space velocity of 120?000 mL g(-1) h(-1) and a relative humidity of 50-90%, 98% removal of 10 ppm NO has been achieved for over 237 h and no sign of deactivation was observed with mesostructured amorphous manganese oxides (AMO), due to the prevention of the catalyst active sites from deactivation. PMID:25728967

  14. Protective effects of antioxidants and anti-inflammatory agents against manganese-induced oxidative damage and neuronal injury

    Microsoft Academic Search

    Dejan Milatovic; Ramesh C. Gupta; Yingchun Yu; Snjezana Zaja-Milatovic; Michael Aschner

    2011-01-01

    Exposure to excessive manganese (Mn) levels leads to neurotoxicity, referred to as manganism, which resembles Parkinson's disease (PD). Manganism is caused by neuronal injury in both cortical and subcortical regions, particularly in the basal ganglia. The basis for the selective neurotoxicity of Mn is not yet fully understood. However, several studies suggest that oxidative damage and inflammatory processes play prominent

  15. Electronic transport in Lithium Nickel Manganese Oxide, a high-voltage cathode material for Lithium-Ion batteries

    E-print Network

    Ransil, Alan Patrick Adams

    2013-01-01

    Potential routes by which the energy densities of lithium-ion batteries may be improved abound. However, the introduction of Lithium Nickel Manganese Oxide (LixNi1i/2Mn3/2O4, or LNMO) as a positive electrode material appears ...

  16. Understanding the role of manganese dioxide in the oxidation of phenolic compounds by aqueous permanganate.

    PubMed

    Jiang, Jin; Gao, Yuan; Pang, Su-Yan; Lu, Xue-Ting; Zhou, Yang; Ma, Jun; Wang, Qiang

    2015-01-01

    Recent studies have shown that manganese dioxide (MnO2) can significantly accelerate the oxidation kinetics of phenolic compounds such as triclosan and chlorophenols by potassium permanganate (Mn(VII)) in slightly acidic solutions. However, the role of MnO2 (i.e., as an oxidant vs catalyst) is still unclear. In this work, it was demonstrated that Mn(VII) oxidized triclosan (i.e., trichloro-2-phenoxyphenol) and its analogue 2-phenoxyphenol, mainly generating ether bond cleavage products (i.e., 2,4-dichlorophenol and phenol, respectively), while MnO2 reacted with them producing appreciable dimers as well as hydroxylated and quinone-like products. Using these two phenoxyphenols as mechanistic probes, it was interestingly found that MnO2 formed in situ or prepared ex situ greatly accelerated the kinetics but negligibly affected the pathways of their oxidation by Mn(VII) at acidic pH 5. The yields (R) of indicative products 2,4-dichlorophenol and phenol from their respective probes (i.e., molar ratios of product formed to probe lost) under various experimental conditions were quantified. Comparable R values were obtained during the treatment by Mn(VII) in the absence vs presence of MnO2. Meanwhile, it was confirmed that MnO2 could accelerate the kinetics of Mn(VII) oxidation of refractory nitrophenols (i.e., 2-nitrophenol and 4-nitrophenol), which otherwise showed negligible reactivity toward Mn(VII) and MnO2 individually, and the effect of MnO2 was strongly dependent upon its concentration as well as solution pH. These results clearly rule out the role of MnO2 as a mild co-oxidant and suggest a potential catalytic effect on Mn(VII) oxidation of phenolic compounds regardless of their susceptibility to oxidation by MnO2. PMID:25437924

  17. Purification and Characterization of the Manganese(II) Oxidizing Protein from Erythrobacter sp. SD-21

    NASA Astrophysics Data System (ADS)

    Nakama, K. R.; Lien, A.; Johnson, H. A.

    2013-12-01

    The manganese(II) oxidizing protein (Mop) found in the alpha-proteobacterium Erythrobacter sp. SD-21 catalyzes the formation of insoluble Mn(III/IV) oxides from soluble Mn(II). These Mn(III/IV) oxides formed are one of the strongest naturally occurring oxides, next to oxygen, and can be used to adsorb and oxidize toxic chemicals from the surrounding environment. Because of the beneficial use in the treatment of contaminated sources, the mechanism and biochemical properties of this novel enzyme are being studied. Due to low expression levels in the native host strain, purification of Mop has been problematic. To overcome this problem the gene encoding Mop, mopA, was cloned from the native host into a C-terminal histidine tag vector and expressed in Escherichia coli cells. Affinity chromatography under denaturing conditions have been applied in attempts to purify an active Mop. Western blots have confirmed that the protein is being expressed and is at the expected size of 250 kDa. Preliminary characterization on crude extract containing Mop has shown a Km and vmax value of 2453 uM and 0.025 uM min-1, respectively. Heme and pyrroloquinoline quinone can stimulate Mn(II) oxidizing activity, but hydrogen peroxide does not affect activity, despite the sequence similarity to animal heme peroxidase proteins. Research has been shown that calcium is essential for Mop activity. Purifying an active Mn(II) oxidizing protein will allow for a better understanding behind the enigmatic process of Mn(II) oxidation.

  18. Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

    USGS Publications Warehouse

    Hem, J.D.; Lind, C.J.

    1991-01-01

    Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn2+ and Cd2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd2Mn34+O8, Mn2+2Mn4+3O8, MnO2 (ramsdellite), and CdCO3. Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn2+Mn23+O4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35??C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn4+ oxide formation in the presence of Cd2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn2O4 Int, an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn3+ ions. The Mn2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn2+ to Mn4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd2Mn3O8 and MnO2 increased at the expense of other precipitate components. ?? 1991.

  19. Preparation of poly(aniline-co-o-anisidine)-intercalated mesostructured manganese oxide composites by exchange reaction

    SciTech Connect

    Wang Gengchao [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)], E-mail: gengchaow@ecust.edu.cn; Yang Zhenyu; Li Xingwei; Li Chunzhong [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Yuan Weikang [UNILAB, State Key Laboratory of Chemical Reaction Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2008-08-04

    Layered mesostructured manganese oxide (mesostructured MnO{sub 2}) was synthesized using manganese chloride and lithium hydroxide as the raw materials and cetyltrimethylammonium bromide (CTAB) as the structure-directing agent. Poly(aniline-co-o-anisidine)-intercalated mesostructured MnO{sub 2} composites (P(An-co-oAs)/MnO{sub 2}) were synthesized in an organic solvent through the exchange reaction between the CTAB in MnO{sub 2} gallery and the P(An-co-oAs). The interlayer spacing (I{sub c} values) of mesostructured MnO{sub 2} enlarged from 2.52 to 4.41 nm as the added amount of P(An-co-oAs) increased from 0 to 0.5 g per 0.5 g of mesostructured MnO{sub 2}. The regularity of the layered structure of the composites was firstly decreased due to intercalation of low amounts of P(An-co-oAs). However, with increasing the intercalated amount of P(An-co-oAs) the layered structure of the composites becomes more regular. The electrical conductivity of the composites is 10{sup 2} to 10{sup 3} times higher than that of the mesostructured MnO{sub 2}.

  20. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    SciTech Connect

    Štengl, Václav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic) [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); J.E. Purkyn? University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Grygar, TomᚠMatys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic) [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); J.E. Purkyn? University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Bludská, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic)] [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); Opluštil, František; N?mec, Tomᚠ[Military Technical Institute of Protection Brno, Vesla?ská 230, 628 00 Brno (Czech Republic)] [Military Technical Institute of Protection Brno, Vesla?ská 230, 628 00 Brno (Czech Republic)

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ? New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ? The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ? One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

  1. Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li+ recovery.

    PubMed

    Yu, Qianqian; Sasaki, Keiko; Hirajima, Tsuyoshi

    2013-11-15

    Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li(+). Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li(+) adsorption. The optimized sample was obtained after calcination at 500 °C for 4h, which shows higher Li(+) adsorption capacity than particulate materials. PMID:24007997

  2. Intermediates of a polynuclear manganese center involved in photosynthetic oxidation of water

    PubMed Central

    Dismukes, G. Charles; Siderer, Yona

    1981-01-01

    Electron paramagnetic resonance of spinach chloroplasts given a series of laser flashes, n = 0, 1,..., 6, at room temperature and rapidly cooled to -140°C reveals a signal possessing at least 16 and possibly 21 or more hyperfine lines when observed below 35 K. The spectrum is consistent with a pair of antiferromagnetically coupled Mn ions, or possibly a tetramer of Mn ions, in which Mn(III) and Mn(IV) oxidation states are present. The intensity of this signal peaks on the first and fifth flashes, suggesting a cyclic change in oxidation state of period 4. The multiline signal produced on the first flash is not affected by the electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea but is abolished by agents that influence the state of bound manganese, such as incubation with alkaline Tris, or dithionite, and by extraction with cholate detergent in the presence of ammonium sulfate. These results indicate that the paramagnetic signal is monitoring oxidation state changes in the enzyme involved in oxidation of water. PMID:16592949

  3. Heterologous expression and characterization of the manganese-oxidizing protein from Erythrobacter sp. strain SD21.

    PubMed

    Nakama, Katherine; Medina, Michael; Lien, Ahn; Ruggieri, Jordan; Collins, Krystle; Johnson, Hope A

    2014-11-01

    The manganese (Mn)-oxidizing protein (MopA) from Erythrobacter sp. strain SD21 is part of a unique enzymatic family that is capable of oxidizing soluble Mn(II). This enzyme contains two domains, an animal heme peroxidase domain, which contains the catalytic site, followed by a C-terminal calcium binding domain. Different from the bacterial Mn-oxidizing multicopper oxidase enzymes, little is known about MopA. To gain a better understanding of MopA and its role in Mn(II) oxidation, the 238-kDa full-length protein and a 105-kDa truncated protein containing only the animal heme peroxidase domain were cloned and heterologously expressed in Escherichia coli. Despite having sequence similarity to a peroxidase, hydrogen peroxide did not stimulate activity, nor was activity significantly decreased in the presence of catalase. Both pyrroloquinoline quinone (PQQ) and hemin increased Mn-oxidizing activity, and calcium was required. The Km for Mn(II) of the full-length protein in cell extract was similar to that of the natively expressed protein, but the Km value for the truncated protein in cell extract was approximately 6-fold higher than that of the full-length protein, suggesting that the calcium binding domain may aid in binding Mn(II). Characterization of the heterologously expressed MopA has provided additional insight into the mechanism of bacterial Mn(II) oxidation, which will aid in understanding the role of MopA and Mn oxidation in bioremediation and biogeochemical cycling. PMID:25172859

  4. Aerobic oxidation of anthracene in the presence of manganese porphyrinates and NaBH/sub 4/ reducing agent

    SciTech Connect

    Lukashova, E.A.; Solov'ev, A.B.; Chugreev, A.L.; Enikolopyan, N.S.

    1987-12-01

    The authors investigate the kinetics of anthracene oxidation by molecular oxygen in the presence of manganese, iron, and cobalt porphyrinate catalysts and a sodium borohydride reducing agent at room temperature in solutions of ethanol or ethanol with chloroform and benzene. Effective rate constants for the reactions are determined based on the amount of anthraquinone formed in the reaction. In all cases with the exception of cobalt tetraphenylporphyrinate the only oxidation product was anthraquinone. Its structure was verified by NMR and IR spectroscopy.

  5. Manganese peroxidase from the basidiomycete Phanerochaete chrysosporium: spectral characterization of the oxidized states and the catalytic cycle

    Microsoft Academic Search

    Hiroyuki Wariishi; Lakshmi Akileswaran; Michael H. Gold

    1988-01-01

    Manganese peroxidase (MnP), an extracellular heme enzyme from the lignin-degrading fungus Phanerochaete chrysosporium, catalyzes the Mn(II)-dependent oxidation of a variety of phenols. Herein, the authors spectroscopically characterize the oxidized states of MnP compounds I, II, and III and clarify the role of Mn in the catalytic cycle of the enzyme. Addition of 1 equiv of HâOâ to the native ferric

  6. Design, synthesis, and characterization of materials for controlled line deposition, environmental remediation, and doping of porous manganese oxide material

    Microsoft Academic Search

    Craig A. Calvert

    2008-01-01

    This thesis covers three topics: (1) coatings formed from sol-gel phases, (2) environmental remediation, and (3) doping of a porous manganese oxide. Synthesis, characterization, and application were investigated for each topic. Line-formations were formed spontaneously by self-assembly from vanadium sol-gels and other metal containing solutions on glass substrates. The solutions were prepared by the dissolution of metal oxide or salt

  7. THEORETICAL TECHNIQUE FOR DETERMINING THE CUMULATIVE IMPACT OF IRON AND MANGANESE OXIDATION IN STREAMS RECEIVING COAL-MINE DISCHARGE.

    USGS Publications Warehouse

    Bobay, Keith E.; Banaszak, Konrad J.

    1985-01-01

    Two U. S. Geological Survey computer programs are modified and linked to predict the cumulative impact of iron and manganese oxidation in coal-mine discharge on the dissolved-chemical quality of a receiving stream. The coupled programs calculate the changes in dissolved-iron, dissolved-manganese, and dissolved-oxygen concentrations, and the pH of surface water downstream from the discharge. The cumulative impact of representative discharges from several coal mines on stream quality in a small watershed in southwestern Indiana was simulated to determine the effectiveness and sensitivity of the coupled programs.

  8. Highly efficient oxidation of secondary alcohols to ketones catalyzed by manganese complexes of N4 ligands with H2O2.

    PubMed

    Shen, Duyi; Miao, Chengxia; Xu, Daqian; Xia, Chungu; Sun, Wei

    2015-01-01

    The manganese complex Mn(S-PMB)(CF3SO3)2 was proven to be highly efficient in the catalytic oxidation of several benzylic and aliphatic secondary alcohols with H2O2 as the oxidant and acetic acid as the additive. A maximum turnover number of 4700 was achieved in the alcohol oxidation. In addition, the Hammett analysis unveiled the electrophilic nature of this manganese catalyst with N4 ligand. PMID:25513725

  9. Light-induced multistep oxidation of dinuclear manganese complexes for artificial photosynthesis

    Microsoft Academic Search

    Ping Huang; Joakim Högblom; Magnus F. Anderlund; Licheng Sun; Ann Magnuson; Stenbjörn Styring

    2004-01-01

    Two dinuclear manganese complexes, [Mn2BPMP(?-OAc)2]·ClO4 (1, where BPMP is the anion of 2,6-bis{[N,N-di(2-pyridinemethyl)amino]methyl}-4-methylphenol) and [Mn2L(?-OAc)2]·ClO4 (2, where L is the trianion of 2,6-bis{[N-(2-hydroxy-3,5-di-tert-butylbenzyl)-N-(2-pyridinemethyl)amino]methyl}-4-methylphenol), undergo several oxidations by laser flash photolysis, using rutheniumII-tris-bipyridine (tris(2,2-bipyridyl)dichloro-ruthenium(II) hexahydrate) as photo-sensitizer and penta-amminechlorocobalt(III) chloride as external electron acceptor. In both complexes stepwise electron transfer was observed. In 1, four Mn-valence states from the initial Mn2II,II

  10. Electron microscopy study of a manganese-doped holmium zirconium oxide solid solution

    SciTech Connect

    Nakano, Hiromi; Shirakami, Tatsuya; Urabe, Kazuyori [Ryukoku Univ., Seta, Otsu (Japan)] [Ryukoku Univ., Seta, Otsu (Japan); Matsuo, Akiro; Kamegashira, Naoki [Toyohashi Univ. of Technology (Japan). Dept. of Materials Science] [Toyohashi Univ. of Technology (Japan). Dept. of Materials Science

    1998-12-01

    A new material, manganese-doped holmium zirconium oxide solid solution, was synthesized in a reducing atmosphere at 1623 K. Microstructural characterization of the material was performed using transmission electron microscopy (TEM) in conjunction with energy-dispersive X-ray spectroscopy (EDXS). It was confirmed that the material consisted of two phases having a similar basic cell related to the fluorite-type structure. One of the phases builds up the matrix and reveals the fluorite-type structure. The other phase has a structural modulation along the <110> direction of the basic cell, with spacing two times that of the (110) plane, and occurs as small precipitates, 70--100 nm in size, embedded in the matrix. A lattice correspondence was maintained between the precipitates and the matrix with a small strain. The holmium content in the precipitates is higher than that of the matrix, which gives rise to the structure modulation along the <110> direction.

  11. Doubling the capacity of lithium manganese oxide spinel by a flexible skinny graphitic layer.

    PubMed

    Noh, Hyun Kuk; Park, Han-Saem; Jeong, Hu Young; Lee, Sang Uck; Song, Hyun-Kon

    2014-05-12

    By coating nanoparticular lithium manganese oxide (LMO) spinel with a few layers of graphitic basal planes, the capacity of the material reached up to 220?mA?h?g(-1) at a cutoff voltage of 2.5?V. The graphitic layers 1)?provided a facile electron-transfer highway without hindering ion access and, more interestingly, 2)?stabilized the structural distortion at the 3?V region reaction. The gain was won by a simple method in which microsized LMO was ball-milled in the presence of graphite with high energy. Vibratory ball milling pulverized the LMO into the nanoscale, exfoliated graphite of less than 10?layers and combined them together with an extremely intimate contact. Ab?initio calculations show that the intrinsically very low electrical conductivity of the tetragonal phase of the LMO is responsible for the poor electrochemical performance in the 3?V region and could be overcome by the graphitic skin strategy proposed. PMID:24706561

  12. Search for new manganese-cobalt oxides as positive electrode materials for lithium batteries P. Strobel, J. Tillier, A. Diaz, A. Ibarra-Palos, F. Thiry and J.B. Soupart *

    E-print Network

    Boyer, Edmond

    Search for new manganese-cobalt oxides as positive electrode materials for lithium batteries P new mixed manganese-cobalt oxides for lithium battery positive electrode materials were obtained using by cheaper and environmentally friendlier elements. Manganese is one of the most attractive alternates

  13. Impact of surfactant-induced wettability alterations on DNAPL invasion in quartz and iron oxide-coated sand systems.

    PubMed

    Molnar, Ian L; O'Carroll, Denis M; Gerhard, Jason I

    2011-01-25

    Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture. PMID:20880604

  14. Polyvinylpyrrolidone/reduced graphene oxide nanocomposites thin films coated on quartz crystal microbalance for NO2 detection at room temperature

    NASA Astrophysics Data System (ADS)

    Huang, Junlong; Xie, Guangzhong; Zhou, Yong; Xie, Tao; Tai, HuiLing; Yang, Guangjin

    2014-08-01

    Polyvinylpyrrolidone (PVP)/reduced graphene oxide (RGO) nanocomposites are sprayed on quartz crystal microbalance (QCM) for NO2 sensing. The thin films are characterized by Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy (UV-VIS). The experimental results reveal that PVP/RGO sensor exhibits higher sensitivity and shorter recovery time than those of PVP. Besides, the response to 20 ppm NO2 is higher than other gases such as CO, CO2 and NH3 even at 100ppm. When the PVP/RGO sensor is exposed to these gases, the good selectivity to NO2 makes the sensor ideal for NO2 detection.

  15. The effect of different metal ions between nanolayers of manganese oxide on water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Ghobadi, Mohadeseh Zarei; Amini, Emad; Haghighi, Behzad

    2014-12-01

    Here, we used a strategy to answer to the question that whether Ca(II) ion is specific for water oxidation or not? In the procedure, first we synthesized layered Mn oxides with K(I) between layers and then replaced K(I) by Ca(II), K(I), Mg(II), La(III) or Ni(II). We proposed that Ca(II), K(I), Mg(II), La(III) and Ni(II), between layers are important to form efficient water-oxidizing catalyst, but not specific in water oxidation. However, Cu(II) ions decrease water-oxidizing activity of layered Mn oxides. The result is important to find critical factors in water oxidation by low-cost and environmentally friendly nanolayered Mn oxides. PMID:25463674

  16. Early diagenetic processes generate iron and manganese oxide layers in the sediments of Lake Baikal, Siberia.

    PubMed

    Torres, Natascha T; Och, Lawrence M; Hauser, Peter C; Furrer, Gerhard; Brandl, Helmut; Vologina, Elena; Sturm, Michael; Bürgmann, Helmut; Müller, Beat

    2014-04-01

    Distinct layers of iron(III) and manganese(IV) (Fe/Mn) oxides are found buried within the reducing part of the sediments in Lake Baikal and cause considerable complexity and steep vertical gradients with respect to the redox sequence. For the on-site investigation of the responsible biogeochemical processes, we applied filter tube samplers for the extraction of sediment porewater combined with a portable capillary electrophoresis instrument for the analyses of inorganic cations and anions. On the basis of the new results, the sequence of diagenetic processes leading to the formation, transformation, and dissolution of the Fe/Mn layers was investigated. With two exemplary cores we demonstrate that the dissolution of particulate Fe and Mn is coupled to the anaerobic oxidation of CH? (AOM) either via the reduction of sulphate (SO?(2-)) and the subsequent generation of Fe(II) by S(-II) oxidation, or directly coupled to Fe reduction. Dissolved Fe(II) diffuses upwards to reduce particulate Mn(IV) thus forming a sharp mineral boundary. An alternative dissolution pathway is indicated by the occurrence of anaerobic nitrification of NH?(+) observed at locations with Mn(IV). Furthermore, the reasons and consequences of the non-steady-state sediment pattern and the resulting redox discontinuities are discussed and a suggestion for the burial of active Fe/Mn layers is presented. PMID:24619231

  17. Oxidation of wheat straw lignin by fungal lignin peroxidase, manganese peroxidase and laccase: A comparative study

    SciTech Connect

    Martinez-Ingo, M.J.; Kurek, B. [Laboratorie de Chimie Biologique, Thiverval-Grignon (France)

    1996-10-01

    Lignin peroxidase (LiP), manganese peroxidase (MnP) from Phanerochaete chrysosporium and laccase from Pleurotus eryngii were separately used to degrade alkali wheat straw lignin (AL). In order to characterize the catalytic action of the different enzymes, the chemical structure and the hydrodynamic properties of the treated lignin were analyzed by thioacidolysis-gas chromatography and molecular size exclusion chromatography. The results confirmed that only LiP was able to degrade guiacyl (G) and syringyl (S) structures in non-phenolic methylated lignins. However, provided that some phenolic terminal structures are present, MnP and laccase were able to degrade the non-phenolic portion of the polymer linked by {beta}-O-4 alkyl aryl ether bonds. This suggested that the oxidative reactions catalyzed in alkali straw lignin could progress through bond cleavages generating phenoxy radicals. The molecular size distribution of both thioacidolysis products and the oxidized polymer showed that AL underwent condensation side-reactions regardless of the enzyme treatment, but only LiP oxidation led to the increase in the hydrodynamic volume of the recovered lignin. This indicated that modification of enzymes by bonding patterns in lignin is not always associated with alterations in the spatial network of the polymer.

  18. Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury

    PubMed Central

    Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira

    2013-01-01

    Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

  19. In depth analysis of apoptosis induced by silica coated manganese oxide nanoparticles in vitro.

    PubMed

    Yu, Chao; Zhou, Zhiguo; Wang, Jun; Sun, Jin; Liu, Wei; Sun, Yanan; Kong, Bin; Yang, Hong; Yang, Shiping

    2015-02-11

    Manganese oxide nanoparticles (MnO NPs) have been regarded as a new class of T1-positive contrast agents. The cytotoxicity of silica coated MnO NPs (MnO@SiO2 NPs) was investigated in human cervical carcinoma cells (HeLa) and mouse fibroblast cells (L929). The changes of cell viability, cell morphology, cellular oxidative stress, mitochondrial membrane potential and cell cycle induced by MnO@SiO2 NPs were evaluated. Compared to HeLa cells, L929 cells showed lower cell viability, more strongly response to oxidative stress and higher percentage in the G2/M phase of cell cycle. The appearance of sub-G1 peak, double staining with Annexin V-FITC/PI and the increase of Caspase-3 activity further confirmed apoptosis should be the major form of cell death. Moreover, the apoptotic pathway was clarified as follows. Firstly, reactive oxygen species (ROS) is generated induced by MnO@SiO2 NPs, then p53 is activated followed by an increase in the bax and a decrease in the bcl-2, ultimately leading to G2/M phase arrest, increasing the activity of caspase-3 and inducing apoptosis. PMID:25464291

  20. Manganese Doping of Magnetic Iron Oxide Nanoparticles: Tailoring Surface Reactivity for a Regenerable Heavy Metal Sorbent

    SciTech Connect

    Warner, Cynthia L.; Chouyyok, Wilaiwan; Mackie, Katherine E.; Neiner, Doinita; Saraf, Laxmikant; Droubay, Timothy C.; Warner, Marvin G.; Addleman, Raymond S.

    2012-02-28

    A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described. The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material. Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity. The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl). Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison. The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles. The Mn-doped iron oxide nanoparticles were able to load 1 ppm of Cd followed by complete stripping and recovery of the Cd with a mild acid wash. The Cd loading and stripping is shown to be consistent through multiple cycles with no loss of sorbent performance.

  1. Oxidative stress tolerance is manganese (Mn(2+)) regulated in Streptococcus gordonii.

    PubMed

    Jakubovics, Nicholas S; Smith, Anthony W; Jenkinson, Howard F

    2002-10-01

    The Sca permease in the oral bacterium Streptococcus gordonii is a member of a family of ATP-binding cassette (ABC)-type transporters for manganese (Mn(2+)) and related cations that are associated with streptococcal virulence in a number of infection models. Since Mn(2+) has a protective function against oxidative damage in a variety of bacteria, we have investigated the role of Sca permease in oxidative stress tolerance in Streptococcus gordonii. A single Mn(2+)-dependent superoxide dismutase (SOD), encoded by sodA, is expressed by S. gordonii and was >10-fold up-regulated under oxidative stress conditions. Inactivation of sodA resulted in increased susceptibility of S. gordonii cells to growth inhibition by dioxygen (O(2)), and to killing by paraquat (a superoxide anion generator) and by hydrogen peroxide (H(2)O(2)). Expression of thiol peroxidase, encoded by the tpx gene located immediately downstream of the scaCBA operon, was also up-regulated under oxidative conditions. Inactivation of tpx led to increased susceptibility of cells to H(2)O(2), but not to O(2) or paraquat. In low-Mn(2+) medium (0.01 micro M Mn(2+)) sodA and tpx genes were transcriptionally down-regulated, SOD activity was reduced and cells were more sensitive to growth inhibition by O(2). A Sca permease-deficient (scaC) mutant showed further reduced SOD activity and hypersensitivity to O(2) in medium containing <0.1 micro M Mn(2+). These results demonstrate that the Sca (Mn(2+)) permease in S. gordonii is essential for protection against oxidative stress. PMID:12368459

  2. Superoxide Production by a Manganese-Oxidizing Bacterium Facilitates Iodide Oxidation

    PubMed Central

    Li, Hsiu-Ping; Daniel, Benjamin; Creeley, Danielle; Grandbois, Russell; Zhang, Saijin; Xu, Chen; Ho, Yi-Fang; Schwehr, Kathy A.; Kaplan, Daniel I.; Santschi, Peter H.; Hansel, Colleen M.

    2014-01-01

    The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I?), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2?). In the absence of Mn2+, Roseobacter sp. AzwK-3b cultures oxidized ?90% of the provided iodide (10 ?M) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments. PMID:24561582

  3. Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

    Microsoft Academic Search

    Heather L. Buss; Peter B. Sak; Samuel M. Webb; Susan L. Brantley

    2008-01-01

    In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2–2m thick zone of partially weathered rock layers (?2.5cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ?V of reaction builds up elastic strain energy. The rates

  4. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    PubMed

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx ) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx /AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5?%) in ?-MnO2 /AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure ?-MnO2 . PMID:25284796

  5. Manganese Oxidation State as a Cause of Irritant Patch Test Reactions

    PubMed Central

    Shallcross, Laurie; Ritchie, Simon; Harberts, Erin; Tammaro, Antonella; Gaitens, Joanna; Gaspari, Anthony A.

    2015-01-01

    Background Manganese chloride (MnCl2) 2.5% is included in the extended metals patch test series to evaluate patients for contact hypersensitivity to this metal salt. Objectives The objective of this study was to prospectively determine the rate of allergic and irritant patch test reactions to MnCl2 (Mn(II)), Mn2O3 (Mn(III)), and KMnO4 (Mn(VII)) in a cohort of patients undergoing patch testing. Methods Fifty-eight patients were patch tested with MnCl2, Mn2O3, and KMnO4, each at 2.5% in petrolatum. Patch readings were taken at 48, and 72 or 96 hours, and scored using standard methods. Cultured monolayers of keratinocytes (KCs) were exposed to MnCl2, Mn2O3, and KMnO4 in aqueous culture medium, and cell survival and cytokine release were studied. Conclusions MnCl2 caused irritant patch test reactions in 41% of the cohort, whereas Mn2O3 and KMnO4 caused a significantly lower rate of irritant reactions (both 3%). No allergic morphologies were observed. Similarly, in cultured KC monolayers, only MnCl2 was cytotoxic to KC and induced tumor necrosis factor ? release. The oxidation state of manganese used for patch testing affects the irritancy of this metal salt, as Mn(II) caused an unacceptably high rate of irritant reactions in a cohort of patients. In vitro studies confirmed these clinical data, as only Mn(II) was cytotoxic to cultured monolayers of KC. PMID:24603521

  6. Curcumin protects against cytotoxic and inflammatory effects of quartz particles but causes oxidative DNA damage in a rat lung epithelial cell line

    SciTech Connect

    Li Hui; Berlo, Damien van; Shi Tingming [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Speit, Guenter [Institute of Human Genetics, University of Ulm (Germany); Knaapen, Ad M. [Department of Health Risk Analysis and Toxicology, Nutrition and Toxicology Research Institute Maastricht (NUTRIM), University of Maastricht (Netherlands); Borm, Paul J.A. [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Centre for Expertise in Life Sciences, Zuyd University, Heerlen (Netherlands); Albrecht, Catrin [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Schins, Roel P.F. [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany)], E-mail: roel.schins@uni-duesseldorf.de

    2008-02-15

    Chronic inhalation of high concentrations of respirable quartz particles has been implicated in various lung diseases including lung fibrosis and cancer. Generation of reactive oxygen species (ROS) and oxidative stress is considered a major mechanism of quartz toxicity. Curcumin, a yellow pigment from Curcuma longa, has been considered as nutraceutical because of its strong anti-inflammatory, antitumour and antioxidant properties. The aim of our present study was to investigate whether curcumin can protect lung epithelial cells from the cytotoxic, genotoxic and inflammatory effects associated with quartz (DQ12) exposure. Electron paramagnetic resonance (EPR) measurements using the spin-trap DMPO demonstrated that curcumin reduces hydrogen peroxide-dependent hydroxyl-radical formation by quartz. Curcumin was also found to reduce quartz-induced cytotoxicity and cyclooxygenase 2 (COX-2) mRNA expression in RLE-6TN rat lung epithelial cells (RLE). Curcumin also inhibited the release of macrophage inflammatory protein-2 (MIP-2) from RLE cells as observed upon treatment with interleukin-1 beta (IL-1{beta}) and tumour necrosis factor-alpha (TNF{alpha}). However, curcumin failed to protect the RLE cells from oxidative DNA damage induced by quartz, as shown by formamidopyrimidine glycosylase (FPG)-modified comet assay and by immunocytochemistry for 8-hydroxydeoxyguanosine. In contrast, curcumin was found to be a strong inducer of oxidative DNA damage itself at non-cytotoxic and anti-inflammatory concentrations. In line with this, curcumin also enhanced the mRNA expression of the oxidative stress response gene heme oxygenase-1 (ho-1). Curcumin also caused oxidative DNA damage in NR8383 rat alveolar macrophages and A549 human lung epithelial cells. Taken together, these observations indicate that one should be cautious in considering the potential use of curcumin in the prevention or treatment of lung diseases associated with quartz exposure.

  7. Spatially Resolved Characterization of Biogenic Manganese Oxide Production within a Bacterial Biofilm

    PubMed Central

    Toner, Brandy; Fakra, Sirine; Villalobos, Mario; Warwick, Tony; Sposito, Garrison

    2005-01-01

    Pseudomonas putida strain MnB1, a biofilm-forming bacterial culture, was used as a model for the study of bacterial Mn oxidation in freshwater and soil environments. The oxidation of aqueous Mn+2 [Mn+2(aq)] by P. putida was characterized by spatially and temporally resolving the oxidation state of Mn in the presence of a bacterial biofilm, using scanning transmission X-ray microscopy (STXM) combined with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Mn L2,3 absorption edges. Subsamples were collected from growth flasks containing 0.1 and 1 mM total Mn at 16, 24, 36, and 48 h after inoculation. Immediately after collection, the unprocessed hydrated subsamples were imaged at a 40-nm resolution. Manganese NEXAFS spectra were extracted from X-ray energy sequences of STXM images (stacks) and fit with linear combinations of well-characterized reference spectra to obtain quantitative relative abundances of Mn(II), Mn(III), and Mn(IV). Careful consideration was given to uncertainty in the normalization of the reference spectra, choice of reference compounds, and chemical changes due to radiation damage. The STXM results confirm that Mn+2(aq) was removed from solution by P. putida and was concentrated as Mn(III) and Mn(IV) immediately adjacent to the bacterial cells. The Mn precipitates were completely enveloped by bacterial biofilm material. The distribution of Mn oxidation states was spatially heterogeneous within and between the clusters of bacterial cells. Scanning transmission X-ray microscopy is a promising tool for advancing the study of hydrated interfaces between minerals and bacteria, particularly in cases where the structure of bacterial biofilms needs to be maintained. PMID:15746332

  8. Overexpression of manganese superoxide dismutase protects lung epithelial cells against oxidant injury.

    PubMed

    Ilizarov, A M; Koo, H C; Kazzaz, J A; Mantell, L L; Li, Y; Bhapat, R; Pollack, S; Horowitz, S; Davis, J M

    2001-04-01

    To determine whether overexpression of antioxidant enzymes in lung epithelial cells prevents damage from oxidant injury, stable cell lines were generated with complementary DNAs encoding manganese superoxide dismutase (MnSOD) and/or catalase (CAT). Cell lines overexpressing MnSOD, CAT, or MnSOD + CAT were assessed for tolerance to hyperoxia or paraquat. After exposure to 95% O(2) for 10 d, 44 to 57% of cells overexpressing both MnSOD and CAT and 37 to 47% of cells overexpressing MnSOD alone were viable compared with 7 to 12% of empty vector or parental cells (P < 0.05). To assess if viable cells were capable of cell division after hyperoxic exposures (up to 5 d), a clonogenicity assay was performed. The clonogenic potential of cells overexpressing MnSOD + CAT and MnSOD alone were significantly better than those expressing CAT alone or empty vector controls. In addition, 54 to 72% of cells overexpressing both MnSOD and CAT survived in 1 mM paraquat compared with 58 to 73% with MnSOD alone and 27% with control cells. Overexpression of CAT alone did not improve survival in hyperoxia or paraquat. The combination of MnSOD + CAT did not provide additional protection from paraquat. Data demonstrate that overexpression of MnSOD protects cells from oxidant injury and CAT offers additional protection from hyperoxic injury when co-expressed with MnSOD. PMID:11306437

  9. Manganese peroxidase degrades pristine but not surface-oxidized (carboxylated) single-walled carbon nanotubes.

    PubMed

    Zhang, Chengdong; Chen, Wei; Alvarez, Pedro J J

    2014-07-15

    The transformation of engineered nanomaterials in the environment can significantly affect their transport, fate, bioavailability, and toxicity. Little is known about the biotransformation potential of single-walled carbon nanotubes (SWNTs). In this study, we compared the enzymatic transformation of SWNTs and oxidized (carboxylated) SWNTs (O-SWNTs) using three ligninolytic enzymes: lignin peroxidase, manganese peroxidase (MnP), and laccase. Only MnP was capable of transforming SWNTs, as determined by Raman spectroscopy, near-infrared spectroscopy, and transmission electron microscopy. Interestingly, MnP degraded SWNTs but not O-SWNTs. The recalcitrance of O-SWNTs to enzymatic transformation is likely attributable to the binding of Mn2+ by their surface carboxyl groups at the enzyme binding site, which inhibits critical steps in the MnP catalytic cycle (i.e., Mn2+ oxidation and Mn3+ dissociation from the enzyme). Our results suggest that oxygen-containing surface functionalities do not necessarily facilitate the biodegradation of carbonaceous nanomaterials, as is commonly assumed. PMID:24988479

  10. 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 (?-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 acidic soil environments.

  11. Development of new nanocomposite based on nanosized-manganese oxide and carbon nanotubes for high performance electrochemical capacitors

    Microsoft Academic Search

    Tarik Bordjiba; Daniel Bélanger

    2010-01-01

    We report the synthesis of a new composite electrode based on nanosized-manganese oxide and carbon nanotubes (CNTs) by electrophoretic deposition of CNTs on a stainless steel (SS) substrate followed by direct spontaneous reduction of MnO4? ions to MnO2 to form the multi-scaled SS–CNT–MnO2 electrode. The resulting material was characterized by scanning electron microscopy, energy dispersive X-ray analysis, cyclic voltammetry and

  12. The oxidation of cyclic alcohols from an aqueous solution by manganese porphyrins embedded in a polydimethylsiloxane membrane

    Microsoft Academic Search

    P. E. F Neys; I. F. J Vankelecom; R. F Parton; W Dehaen; G L'abbé; P. A Jacobs

    1997-01-01

    The use of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato] manganese(III) chloride [TDCPP(Mn)Cl] embedded in polydimethylsiloxane (PDMS) is reported for the oxidation of cyclic alcohols to ketones with t-butylhydroperoxide from an aqueous solution. Two important observations are made which both can be ascribed to the sorption exercised by the polymer. Firstly, compared to a homogeneous set-up much higher activities are reached with the PDMS-system. Secondly, the

  13. Novel Non-Stoichiometric Manganese - Cobalt - Nickel - Oxide Composite as Humidity Sensor Through Solid-State Electrical Conductivity Measurements

    Microsoft Academic Search

    R. SUNDARAM; K. MANIRAJ

    Equimolar amounts of manganese(II) chloride, cobalt(III) nitrate and nickel(II) chloride in aqueous solution were reacted with ammonia and the resulting precipitate of hydroxides was heated to 7500 C in 6h to yield a non stoichiometric oxides having a composition of Mn0.06Co0.6 Ni0.6 O2.5 as analyzed by atomic absorption spectroscopy to a pellet and sintered at 600oC. Characterization of the materia

  14. Electrical resistivity measurements on manganese oxides with layer and tunnel structures: Birnessites, todorokites, and cryptomelanes

    SciTech Connect

    De Guzman, R.N.; Awaluddin, A.; Shen, Y.F. [and others

    1995-07-01

    Direct-current measurements were used to determine the electrical resistivities of several manganese oxide materials having either layered or tunnel structures. Birnessite (Na-OL-1, OL=octahedral layer) consists of layers of edge- and corner-sharing Mn{sub 6} octahedral units with Na{sup +} in the interlayer regions. Todorokite and cryptomelane (Mg-OMS-1 and K-OMS-2, respectively, OMS = octahedral molecular sieve) are similarly built from MnO{sub 6} units, but in these systems the octahedral join to form 6.9 and 4.6 {Angstrom} tunnels occupied by Mg{sup 2+} and K{sup +}, respectively. Resistivities were also measured for OL-1, OMS-1, and OMS-2 materials in which (a) cation exchange was carried out at layer and tunnel sites or (b) isomorphous subsititution for Mn was performed by doping small amounts of foreign cations into the manganese oxide framework. Four probe measurements on pressed pellets reveal that OL-1 and OMS-1 materials have resistivities on the order of 10{sup 5}-10{sup 6} {Omega}cm at 298 K. OMS-2 materials have resistivities on the order of 10{sup 5}-10{sup 6} {Omega} cm at 298 K. Variable-temperature measurements establish a general pattern of increasing resistivity with decreasing temperature. However, between 153 and 293 K, OL-1 and OMS-1 materials do not obey a simple exponential variation of resistivity and temperature. By contrast, OMS-2 samples follow the Arrhenius relationship over a comparable temperature range. Activation energies for the conductivity OMS-2 materials were calculated to be in the range 0.5-0.6 eV. Solid-state voltammetry was used to determine the electrical resistance of OMS-1 and OMS-2 samples at higher temperatures from 298 to 673 K. A general exponential decrease in resistance with increasing temperature was observed for both classes of materials. Ac resistivity measurements show similar trends to dc resistivity data. 36 refs., 8 figs., 3 tabs.

  15. Effect of Copper Oxide and Manganese Oxide on Properties and Low Temperature Degradation of Sintered Y-TZP Ceramic

    NASA Astrophysics Data System (ADS)

    Khan, M. M.; Ramesh, S.; Bang, L. T.; Wong, Y. H.; Ubenthiran, S.; Tan, C. Y.; Purbolaksono, J.; Misran, H.

    2014-09-01

    The effect of copper oxide (CuO) and manganese oxide (MnO2) co-dopant on the densification behavior of 3 mol% yttria-stabilized zirconia was investigated. Green samples were prepared and sintered in air at temperatures ranging from 1250 to 1500 °C with a short holding time of 12 min. Sintered bodies were characterized to determine the phase stability, bulk density, hardness, fracture toughness, Young's modulus and grain size. In addition, the aging-induced tetragonal to monoclinic phase transformation of the sintered zirconia was evaluated. It was revealed that the addition of CuO-MnO2 co-dopant was beneficial in enhancing the densification and mechanical properties of the ceramic particularly at low temperatures. A high fracture toughness of 5.5 MPam1/2 coupled with high hardness of 14.5 GPa was obtained for co-doped samples sintered at 1350 °C. However, the undoped ceramic exhibited better properties when sintered above 1350 °C. The study also found that the dopants did not prevent grain coarsening and hence did not suppress the aging-induced phase transformation particularly for samples sintered above 1350 °C.

  16. Effect of Copper Oxide and Manganese Oxide on Properties and Low Temperature Degradation of Sintered Y-TZP Ceramic

    NASA Astrophysics Data System (ADS)

    Khan, M. M.; Ramesh, S.; Bang, L. T.; Wong, Y. H.; Ubenthiran, S.; Tan, C. Y.; Purbolaksono, J.; Misran, H.

    2014-12-01

    The effect of copper oxide (CuO) and manganese oxide (MnO2) co-dopant on the densification behavior of 3 mol% yttria-stabilized zirconia was investigated. Green samples were prepared and sintered in air at temperatures ranging from 1250 to 1500 °C with a short holding time of 12 min. Sintered bodies were characterized to determine the phase stability, bulk density, hardness, fracture toughness, Young's modulus and grain size. In addition, the aging-induced tetragonal to monoclinic phase transformation of the sintered zirconia was evaluated. It was revealed that the addition of CuO-MnO2 co-dopant was beneficial in enhancing the densification and mechanical properties of the ceramic particularly at low temperatures. A high fracture toughness of 5.5 MPam1/2 coupled with high hardness of 14.5 GPa was obtained for co-doped samples sintered at 1350 °C. However, the undoped ceramic exhibited better properties when sintered above 1350 °C. The study also found that the dopants did not prevent grain coarsening and hence did not suppress the aging-induced phase transformation particularly for samples sintered above 1350 °C.

  17. Oxidation of arsenate(III) with manganese oxides in water treatment

    Microsoft Academic Search

    Wolfgang Driehaus; Reiner Seith; Martin Jekel

    1995-01-01

    Arsenate(III) is the more toxic form of inorganic arsenic and its removal from drinking water is less effective as compared to arsenate(V). Arsenate(III) persists in aerated water, even at high pH, but is easily oxidized by managanese dioxides. The oxidation of As(III) follows a second order rate law with respect to As(III). The reaction rate is effected by the initial

  18. New divalent manganese complex with pyridine carboxylate N-oxide ligand: Synthesis, structure and magnetic properties

    NASA Astrophysics Data System (ADS)

    Liu, Fu-Chen; Xue, Min; Wang, Hai-Chao; Ou-Yang, Jie

    2010-09-01

    Two new manganese complexes, [Mn 3( L1) 4(NO 3) 2] n ( 1, H L1=nicotinate N-oxide acid) and [Mn L2Cl] n ( 2, H L2=isonicotinate N-oxide acid)], have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. In 1, the L1 ligands take two different coordinated modes bridging four and three Mn II ions. The nitrate anions take chelating coordination modes, leading one type of the Mn II ions as a 4-connected node. The whole net can be viewed as a 3, 4, 6-connected 4-nodal net with Schläfli notation {4 3}2{4 4; 6 2}4{4 6; 6 6; 8 3}. Complex 2 has a honeycomb layer mixed bridged by chlorine, N-oxide and carboxylate. The adjacent layers are linked by the phenyl ring of L2 ligand, giving a 3D framework with a {3 4; 5 4} {3 2;4;5 6;6 6} 4, 6-connect net. Magnetic studies indicate that 1 is an antiferromagnet with low-dimensional characteristic, in which a - J1J1J2- coupled alternating chain is predigested. Fitting the data of 1 gives the best parameters J1=-2.77, J2=-0.67 cm -1. The magnetic properties of complex 2 represent the character of the 2D honeycomb layer with the J1=-2.05 and J2=0.55 cm -1, which results in a whole antiferromagnetic state.

  19. Translocation of Inhaled Ultrafine Manganese Oxide Particles to the Central Nervous System

    PubMed Central

    Elder, Alison; Gelein, Robert; Silva, Vanessa; Feikert, Tessa; Opanashuk, Lisa; Carter, Janet; Potter, Russell; Maynard, Andrew; Ito, Yasuo; Finkelstein, Jacob; Oberdörster, Günter

    2006-01-01

    Background Studies in monkeys with intranasally instilled gold ultrafine particles (UFPs; < 100 nm) and in rats with inhaled carbon UFPs suggested that solid UFPs deposited in the nose travel along the olfactory nerve to the olfactory bulb. Methods To determine if olfactory translocation occurs for other solid metal UFPs and assess potential health effects, we exposed groups of rats to manganese (Mn) oxide UFPs (30 nm; ~ 500 ?g/m3) with either both nostrils patent or the right nostril occluded. We analyzed Mn in lung, liver, olfactory bulb, and other brain regions, and we performed gene and protein analyses. Results After 12 days of exposure with both nostrils patent, Mn concentrations in the olfactory bulb increased 3.5-fold, whereas lung Mn concentrations doubled; there were also increases in striatum, frontal cortex, and cerebellum. Lung lavage analysis showed no indications of lung inflammation, whereas increases in olfactory bulb tumor necrosis factor-? mRNA (~ 8-fold) and protein (~ 30-fold) were found after 11 days of exposure and, to a lesser degree, in other brain regions with increased Mn levels. Macrophage inflammatory protein-2, glial fibrillary acidic protein, and neuronal cell adhesion molecule mRNA were also increased in olfactory bulb. With the right nostril occluded for a 2-day exposure, Mn accumulated only in the left olfactory bulb. Solubilization of the Mn oxide UFPs was < 1.5% per day. Conclusions We conclude that the olfactory neuronal pathway is efficient for translocating inhaled Mn oxide as solid UFPs to the central nervous system and that this can result in inflammatory changes. We suggest that despite differences between human and rodent olfactory systems, this pathway is relevant in humans. PMID:16882521

  20. Carbon nanotube-assisted electrodeposition. Part I: Battery performance of manganese oxide films electrodeposited at low current densities

    NASA Astrophysics Data System (ADS)

    Eftekhari, Ali; Molaei, Foroogh

    2015-01-01

    In electrochemical synthesis of manganese oxide, current density has a substantial influence on redox behavior, but less effect on the film morphology. Here we report that a small amount (even not detectable by electron microscopy) of carbon nanotubes can significantly affect the film growth pathway. Although, the galvanostatic syntheses of manganese oxide were similar in the absence and presence of carbon nanotubes, the morphological structures are totally different. This difference is also valid for electrochemical behavior in favor of the formation of a single redox couple. The influence of carbon nanotubes on potentiodynamic electrodeposition of manganese oxide was also similar, leading to the appearance of a strong redox couple without any noticeable capacitive behavior. It should be emphasized that this influence is only valid for the experimental condition under consideration (i.e., low current densities), and electrodeposition at higher current densities in the presence of carbon nanotubes may strengthen the capacitive behavior in favor of supercapacitors (as discussed in the second part). The interesting point is that this tiny additive can predominantly control the electrochemical properties of the system under consideration: supercapacitor or battery.

  1. Manganese enrichment in the Gowganda Formation of the Huronian Supergroup: A highly oxidizing shallow-marine environment after the last Huronian glaciation

    E-print Network

    Manganese enrichment in the Gowganda Formation of the Huronian Supergroup: A highly oxidizing of high levels of O2 during the Great Oxidization Event (GOE). Here we investigate Mn abundance with high Mn/Fe ratios following the appearance of Fe oxides in the Firstbrook Member of the Gowganda

  2. Heavy metals and manganese oxides in the genesee watershed, New York state: effects of geology and land use

    USGS Publications Warehouse

    Whitney, P.R.

    1981-01-01

    Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter. ?? 1981.

  3. A sodium manganese oxide cathode by facile reduction for sodium batteries.

    PubMed

    Song, Jinju; Gim, Jihyeon; Kim, Sungjin; Kang, Jungwon; Mathew, Vinod; Ahn, Docheon; Kim, Jaekook

    2014-06-01

    A nonstoichiometric sodium manganese oxide (Na(x)MnO(2+?)) cathode useful for sodium batteries was synthesized by an ambient-temperature strategy that involved facile reduction of aqueous sodium permanganate in sodium iodide and subsequent heat treatment at 600?°C. Combined powder X-ray diffraction and synchrotron X-ray diffraction analyses confirmed the annealed sample to belong to a Na(x)MnO2 phase with a P2-hexagonal structure. The ICP-AES results confirmed the stoichiometry of the sample to be Na0.53MnO(2+?) . Electron microscopy studies revealed the particle size of the electrode to be in the range of a few hundred nanometers. The Na0.53MnO(2+?) cathode delivered an average discharge capacity of 170?mA?h?g(-1) with a stable plateau at 2.1?V for the initial 25?cycles versus sodium. Ex?situ XANES studies confirmed the reversible intercalation of sodium into Na0.53MnO(2+?) and suggested the accommodation of over-stoichiometric Mn(4+) ions to contribute towards the performance of the electrode. PMID:24692202

  4. Layered manganese oxide intergrowth electrodes for rechargeable lithium batteries: Part 1-substitution with Co or Ni

    SciTech Connect

    Dolle, Mickael; Patoux, Sebastien; Doeff, Marca M.

    2004-09-08

    Lithium manganese oxides substituted with nickel or cobalt were characterized electrochemically in lithium cell configurations. The compounds studied were either single-phase layered structures with either primarily O2 or O3 stacking arrangements, or O2/O3 intergrowths, prepared from P2, P3 and P2/P3 sodium-containing precursors, respectively. The stacking arrangements are extremely sensitive to the Na/T. M. (T. M. = transition metal) ratios and the level of substitution. Phase diagrams showing the stability regions of the various arrangements for the Na-Ni-Mn-O system are presented. A possible correlation between vacancies and electrochemical performance is suggested. For high levels of substitution with Ni, fewer defects are possible for materials containing more O3 component and higher discharge capacities can be achieved, but spinel conversion upon cycling also occurs more rapidly as the O3 content increases. Intergrowths show intermediate behavior and represent a potential route towards designing stable, high capacity electrodes.

  5. Microstructure and supercapacitive properties of buserite-type manganese oxide with a large basal spacing

    NASA Astrophysics Data System (ADS)

    Sun, Zhenjie; Shu, Dong; Chen, Hongyu; He, Chun; Tang, Shaoqing; Zhang, Jie

    2012-10-01

    A hydration-layered structure of buserite-type manganese oxide (Mg-buserite) was successfully synthesized by an ion exchange method. The as-prepared Mg-buserite possesses a large basal spacing of 10 Å, and contains Mg2+ ions and two sheets of water molecules in the interlayer region. The supercapacitive behaviors of Mg-buserite were systematically investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (CD) experiments and electrochemical impedance spectroscopy (EIS). The results showed that the specific capacitance of the Mg-buserite electrode sharply increased during the initial 500 cycles and reached a maximum of 164 F g-1 at approximately the 500th cycle at a scan rate of 1 mV s-1, and then it remained an almost constant value and decreased slightly upon prolonged cycling. After 22,000 cycles, the specific capacitance decreased by approximately 6% of the maximum specific capacitance. The superior capacitive behavior and excellent cycling stability of the as-prepared Mg-buserite are attributed to the large basal spacing, which can accommodate a larger amount of electrolyte cations and provide more favorable pathways for electrolyte cations intercalation and deintercalation. The experimental results demonstrate that Mg-buserite is a promising candidate as an electrode material for supercapacitors.

  6. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

    PubMed

    Pozan, Gulin Selda

    2012-06-30

    The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. ?-Al(2)O(3) and ?-Al(2)O(3) obtained from Boehmite, ?-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/?-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. PMID:22579460

  7. Aluminum manganese oxides with mixed crystal structure: high-energy-density cathodes for rechargeable sodium batteries.

    PubMed

    Han, Dong-Wook; Ku, Jun-Hwan; Kim, Ryoung-Hee; Yun, Dong-Jin; Lee, Seok-Soo; Doo, Seok-Gwang

    2014-07-01

    We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability. PMID:24797956

  8. Solar-thermal Water Splitting Using the Sodium Manganese Oxide Process & Preliminary H2A Analysis

    SciTech Connect

    Todd M. Francis, Paul R. Lichty, Christopher Perkins, Melinda Tucker, Peter B. Kreider, Hans H. Funke, Allan Lewandowski, and Alan W. Weimer

    2012-10-24

    There are three primary reactions in the sodium manganese oxide high temperature water splitting cycle. In the first reaction, Mn2O3 is decomposed to MnO at 1,500°C and 50 psig. This reaction occurs in a high temperature solar reactor and has a heat of reaction of 173,212 J/mol. Hydrogen is produced in the next step of this cycle. This step occurs at 700°C and 1 atm in the presence of sodium hydroxide. Finally, water is added in the hydrolysis step, which removes NaOH and regenerates the original reactant, Mn2O3. The high temperature solar�driven step for decomposing Mn2O3 to MnO can be carried out to high conversion without major complication in an inert environment. The second step to produce H2 in the presence of sodium hydroxide is also straightforward and can be completed. The third step, the low temperature step to recover the sodium hydroxide is the most difficult. The amount of energy required to essentially distill water to recover sodium hydroxide is prohibitive and too costly. Methods must be found for lower cost recovery. This report provides information on the use of ZnO as an additive to improve the recovery of sodium hydroxide.

  9. Relationship of crystal structure to interionic interactions in the lithium-manganese spinel oxides

    PubMed

    Piszora; Catlow; Woodley; Wolska

    2000-07-01

    Lithium manganese oxides in the form of cubic spinel phases (space group Fd3m) are formed in a LixMn3-xO4 system for rather limited values of x. Structural investigations by X-ray powder diffraction, applied to the Li-Mn-O compounds, indicate the formation of a second crystalline phase, Li2MnO3 (space group C2/m), with the increasing lithium content. Total Li+ content per unit cell and the cation distribution over a spinel lattice in LixMn3-xO4 have been studied by measurements of integrated intensities of X-ray reflections, and by structure refinement using Rietveld profile analysis. In an attempt to understand the factors affecting cation distribution in the spinel lattice, we applied the computer modelling techniques and investigated the Li+, Mn3+ and Mn4+ ion distribution by calculating the lattice energy, combined with energy minimisation procedures, using the General Utility Lattice Program (GULP), a program designed for simulation of ionic and semi-ionic solids, based on interatomic potential models. PMID:10890371

  10. Photo-catalytic Degradation and Sorption of Radio-cobalt from EDTA-Co Complexes Using Manganese Oxide Materials - 12220

    SciTech Connect

    Koivula, Risto; Harjula, Risto [University of Helsinki, P.O.Box 55, FI-00014 Helsinki (Finland); Tusa, Esko [Fortum Power and Heat Oy P.O.Box 100, 00048 FORTUM (Finland)

    2012-07-01

    The synthesised cryptomelane-type ?-MnO{sub 2} was tested for its Co-57 uptake properties in UV-photo-reactor filled with 10 ?M Co-EDTA solution with a background of 10 mM NaNO{sub 3}. High cobalt uptake of 96% was observed after 1 hour of UV irradiation. As for comparison, a well-known TiO{sub 2} (Degussa P25) was tested as reference material that showed about 92% cobalt uptake after six hours of irradiation in identical experiment conditions. It was also noted that the cobalt uptake on cryptomelane with out UV irradiation was modest, only about 10%. Decreasing the pH of the Co-EDTA solution had severe effects on the cobalt uptake mainly due to the rather high point of zero charge of the MnO{sub 2} surface (pzc at pH ?4.5). Modifying the synthesis procedure we were able to produce a material that functioned well even in solution of pH 3 giving cobalt uptake of almost 99%. The known properties, catalytic and ion exchange, of manganese oxides were simultaneously used for the separation of EDTA complexed Co-57. Tunnel structured cryptomelane -type showed very fast and efficient Co uptake properties outperforming the well known and widely used Degussa P25 TiO{sub 2} in both counts. The layered structured manganese oxide, birnessite, reached also as high Co removal level as the reference material Degussa did but the reaction rate was considerably faster. Since the decontamination solutions are typically slightly acidic and the point of zero charge of the manganese oxides are rather high > pH 4.5 the material had to be modified. This modified material had tolerance to acidic solutions and it's Co uptake performance remained high in the solutions of lower pH (pH 3). Increasing the ion concentration of test solutions, background concentration, didn't affect the final Co uptake level; however, some changes in the uptake kinetics could be seen. The increase in EDTA/MoMO ratio was clearly reflected in the Co uptake curves. The obtained results of manganese oxide were very promising for the treatment of EDTA complexed Co solutions. The better performance values and cheaper production cost of manganese oxide, compared to titanium dioxide, is so big driving force that further studies on the material are evident. The possibilities for continuous treatment, instead of the fluidized bed -type batch experiment are investigated and the effects of other compounds affecting the de-complexation of Co-EDTA are further studied. (authors)

  11. Aerobic Oxidation of Benzyl Alcohol over Activated Carbon Supported Manganese and Vanadium Catalysts: Effect of Surface Oxygen-Containing Groups

    Microsoft Academic Search

    Yuanting ChenWan; Wan Chen; Qinghu Tang; Zhen Guo; Yanhui Yang; Fabing Su

    2011-01-01

    \\u000a Abstract  In this contribution, the selective oxidation of benzyl alcohol using molecular oxygen over supported manganese and vanadium\\u000a catalysts was investigated. The catalytic activities were significantly improved after pre-oxidizing the activated carbon\\u000a support materials. Characterizations of nitrogen physisorption, X-ray diffraction, transmission electron microscopy, and X-ray\\u000a absorption were involved to examine the physicochemical properties of as-prepared catalysts. By ruling out the effects

  12. New strategy to enhance phosphate removal from water by hydrous manganese oxide.

    PubMed

    Pan, Bingcai; Han, Feichao; Nie, Guangze; Wu, Bing; He, Kai; Lu, Lv

    2014-05-01

    Hydrous manganese oxide (HMO) is generally negatively charged at circumneutral pH and cannot effectively remove anionic pollutants such as phosphate. Here we proposed a new strategy to enhance HMO-mediated phosphate removal by immobilizing nano-HMO within a polystyrene anion exchanger (NS). The resultant nanocomposite HMO@NS exhibited substantially enhanced phosphate removal in the presence of sulfate, chloride, and nitrate at greater levels. This is mainly attributed to the pHpzc shift from 6.2 for the bulky HMO to 10.5 for the capsulated HMO nanoparticles, where HMO nanoparticles are positively charged at neutral pH. The ammonium groups of NS also favor phosphate adsorption through the Donnan effect. Cyclic column adsorption experiment indicated that the fresh HMO@NS could treat 460 bed volumes (BV) of a synthetic influent (from the initial concentration of 2 mg P[PO4(3-)]/L to 0.5 mg P[PO4(3-)]/L), while only 80 BV for NS. After the first time of regeneration by NaOH-NaCl solution, the capacity of HMO@NS was lowered to ? 300 BV and then kept constant for the subsequent 5 runs, implying the presence of both the reversible and irreversible adsorption sites of nano-HMO. Additional column adsorption feeding with a real bioeffluent further validated great potential of HMO@NS in advanced wastewater treatment. This study may provide an alternative approach to expand the usability of other metal oxides in water treatment. PMID:24730751

  13. Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites with excellent decolorization performance

    SciTech Connect

    Zhou, Junli, E-mail: Zhoujunli19851111@163.com [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)] [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Yu, Lin, E-mail: gych@gdut.edu.cn [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)] [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Sun, Ming; Ye, Fei; Lan, Bang; Diao, Guiqiang; He, Jun [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)] [Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)

    2013-02-15

    Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled in the presence of CTAB, and subsequently pillared with Keggin ions. The obtained CTAB-Al-MO with the basal spacing of 1.59 nm could be stable at 300 Degree-Sign C for 2 h and also possesses high total pore volumes (0.41 cm Superscript-Three g{sup -1}) and high specific BET surface area (161 m{sup 2} g{sup -1}), which is nine times larger than that of the pristine (19 m{sup 2} g{sup -1}). Possible formation process for the highly thermal stable CTAB-Al-MO is proposed here. The decolorization experiments of methyl orange showed that the obtained CTAB-Al-MO exhibit excellent performance in wastewater treatment and the decolorization rate could reach 95% within 5 min. - Graphical Abstract: Well-ordered organic-inorganic hybrid LMO nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled by CTAB, and subsequently pillared with Keggin ions. Highlights: Black-Right-Pointing-Pointer A two-step synthesis method was used to prepare the CTAB-Al-MO. Black-Right-Pointing-Pointer The CTAB-Al-MO has the large basal spacing and high specific BET surface area. Black-Right-Pointing-Pointer The thermal stability of the well-ordered CTAB-Al-MO could obviously improve. Black-Right-Pointing-Pointer The CTAB-Al-MO exhibits excellent oxidation and absorption ability to remove organic pollutants.

  14. Effect of Anions on the Binding and Oxidation of Divalent Manganese and Iron in Modified Bacterial Reaction Centers

    PubMed Central

    Tang, Kai; Williams, JoAnn C.; Allen, James P.; Kálmán, László

    2009-01-01

    Abstract The influence of different anions on the binding and oxidation of manganous and ferrous cations was studied in four mutants of bacterial reaction centers that can bind and oxidize these metal ions. Light-minus-dark difference optical and electron paramagnetic resonance spectroscopies were applied to monitor electron transfer from bound divalent metal ions to the photo-oxidized bacteriochlorophyll dimer in the presence of five different anions. At pH 7, bicarbonate was found to be the most effective for both manganese and iron binding, with dissociation constants around 1 ?M in three of the mutants. The pH dependence of the dissociation constants for manganese revealed that only bicarbonate and acetate were able to facilitate the binding and oxidation of the metal ion between pH 6 and 8 where the tight binding in their absence could not otherwise be established. The data are consistent with two molecules of bicarbonate or one molecule of acetate binding to the metal binding site. For ferrous ion, the binding and oxidation was facilitated not only by bicarbonate and acetate, but also by citrate. Electron paramagnetic resonance spectra suggest differences in the arrangement of the iron ligands in the presence of the various anions. PMID:19383473

  15. Iron oxide/manganese oxide co-loaded hybrid nanogels as pH-responsive magnetic resonance contrast agents.

    PubMed

    Wang, Xia; Niu, Dechao; Wu, Qing; Bao, Song; Su, Teng; Liu, Xiaohang; Zhang, Shengjian; Wang, Qigang

    2015-06-01

    This work described a proof of concept study of hybrid nanogel-based magnetic resonance contrast agents, SPIO@GCS/acryl/biotin@Mn-gel, abb. as SGM, for highly efficient, pH-responsive T1 and T2 dual-mode magnetic resonance imaging (MRI). SGM have been synthesized by assembling superparamagnetic iron oxide particles into polysaccharide nanoclusters, followed by in-situ reduction of the manganese species on the clusters and a final mild polymerization. The dual-mode SGM showed an interesting pH-responsiveness in in vitro MRI, with both T1 and T2 relaxivities turned "ON" in the acidic environment, along with an increase in the r1 and r2 relaxivity values by 1.7-fold (from 8.9 to 15.3 mM(-1) S(-1)) and 4.9-fold (from 45.7 to 226 mM(-1) S(-1)), due to desirable silencing and de-silencing effects. This interesting acidic-responsiveness was further verified in vivo with both significantly brightened signal of tumor tissue in T1-weighted MR images and a darkened signal in T2-weighted MR images 50 min post-injection of SGM. This smart hybrid nanogel may serve as a promising candidate for further studies of dual-mode (T1 and T2) contrast agents in MRI, due to its high stability, interesting pH-response mechanism and indicative imaging of tumors. PMID:25890733

  16. Intense photo- and tribo-luminescence of three tetrahedral manganese(II) dihalides with chelating bidentate phosphine oxide ligand.

    PubMed

    Chen, Jun; Zhang, Qing; Zheng, Fa-Kun; Liu, Zhi-Fa; Wang, Shuai-Hua; Wu, A-Qing; Guo, Guo-Cong

    2015-02-21

    Three air-stable tetrahedral manganese(ii) dihalide complexes [MnX2(DPEPO)] (DPEPO = bis[2-(diphenylphosphino)phenyl]ether oxide; X = Cl, Br and I) were prepared. All of the obtained compounds were structurally characterized by single-crystal X-ray diffraction analyses, which reveal that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn(2+) in a tetrahedral environment. Interestingly, these complexes show excellent photoluminescent performance in neat solid form, with the highest total quantum yield (?total) of up to 70% recorded for the dibromide complex. Intense green flashes of light could be observed by the naked eye when rubbing the manganese(ii) complexes. PMID:25597698

  17. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface

    NASA Astrophysics Data System (ADS)

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E.; Nolte, Roeland J. M.; Speller, Sylvia; Amabilino, David B.; de Feyter, Steven; Elemans, Johannes A. A. W.

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  18. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    NASA Astrophysics Data System (ADS)

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries.

  19. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    PubMed Central

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  20. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries.

    PubMed

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  1. Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

    PubMed

    Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Ho?y?ska, Ma?gorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-07-28

    Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6. PMID:24898625

  2. PROGRESS REPORT. TRANSURANIC INTERFACIAL REACTION STUDIES ON MANGANESE OXIDE HYDROXIDE MINERAL SURFACES

    EPA Science Inventory

    Several DOE sites have been contaminated by transuranic radionuclide (TRU) discharges including neptunium and plutonium. Their interaction with the surrounding geological media can affect the transport and remediation of these radionuclides in the environment. Manganese based min...

  3. Synthesis and characterization of novel manganese and vanadium oxides as cathodes for lithium rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Chen, Rongji

    The development of advanced rechargeable lithium batteries depends on cathodes that can reversibly intercalate lithium ions. Intercalation chemistry plays a key role in the electrochemical reduction and oxidation by lithium of many solid electrodes including transition metal compounds. Intercalation compounds such as LixTiS2 and LiCoO2 exhibit some of the ideal characteristics expected of a cathode for advanced batteries. The former shows high rate capability, excellent electronic conductivity and almost perfect reversibility; the latter shows a high voltage suitable for carbon based anodes and good reversibility but an energy density no higher than that of LixTiS2, a prohibitively high cost and an environmental hazard. The spinel LiMn2O4 removes the cost issue but not the others. Thus, much effort has been directed at synthesizing new structures that exhibit enhanced electrochemical activity. Soft chemistry approaches have been applied for this purpose. One such approach is mild hydrothermal reactions which lead to the formation of new metastable transition metal oxides, not accessible by conventional high temperature methods. The nature of the reactants, the pH of the reaction medium, heating temperature and heating duration have dramatic effects on the crystal structure of the phase formed. The mild hydrothermal decomposition of aqueous permanganate solutions has been found to lead to new layered manganese oxides. In the case of alkali permanganates AMnO4, layered birnessite-type compounds are formed with the general formula AxMnO2.nH 2O (A = Li, Na, K). These compounds have R 3¯ m rhombohedral structures analogous to the layered disulfides. The water is reversibly lost on heating, and the compounds readily react with lithium through an intercalation mechanism. The capacity for lithium is a function of the alkali ion present, and the larger potassium ion maintains the capacity best. For the lithium compound, there is a tendency to convert to the spinel structure which leads to loss of capacity. In the case of hydrothermal decomposition of tetramethylammonium permanganate in the presence of nickel, a new structure compound Ni1-xMn1-yO 3 is formed that has a different structure from that of the known ilmenite form. The structure contains empty tunnels into which lithium ions can be intercalated. Reaction of this nickel manganese oxide with n-butyl lithium showed the uptake of 0.91 Li per formula unit. It converts into the known ilmenite form of NiMnO3 at around 400°C. This compound also has interesting magnetic properties. A wide variety of vanadium oxides can be prepared using hydrothermal methods. Organic templates play an important role in directing the structures formed. Although tetramethyl ammonium hydroxide is a widely used organic template, other amines and long chain amine surfactants also yield interesting new structures many of which are layered phases. The hydrothermal reaction of vanadium pentoxide with methylamine leads to a series of new layered vanadium oxides, which differ in structure from the corresponding ones prepared in the presence of the tetramethylammonium ion because of the existence of hydrogen bonding. Methylamine is the first organic to form a double sheet vanadium oxide, (CH3NH3) 0.75V4O10.0.67H2O, with delta-AgxV2O5 structure. (CH 3NH3)V3O7 shows significant buckling of the vanadium oxide layers compared with N(CH3)4V 3O7. Both of these two compounds are monoclinic. (CH 3NH2)2V8O17 has a tetrahedral unit cell and IR shows that the lone pair electrons of nitrogen bond to vanadium. Also, vanadium coordination decreases with an increase in the pH of the reaction medium and hydrogen bonding controls the orientation of the polyhedra in the vanadium sheets, in contrast to the tetramethylammonium ion where the bonding is predominantly ionic.

  4. Biological and Chemical Interactions with U(VI) During Anaerobic Enrichment in the Presence of Iron Oxide Coated Quartz

    SciTech Connect

    Brady D. Lee; Michelle R. Walton; Jodette L. Megio

    2005-11-01

    Microcosm experiments were performed to understand chemical and biological interactions with hexavalent uranium (U(VI)) in the presence of iron oxide bearing minerals and trichloroethylene (TCE) as a co-contaminant. Interactions of U(VI) and hydrous iron oxide moieties on the mineral oxide surfaces were studied during enrichments for dissimilatory iron reducing (DIRB) and sulfate reducing bacteria (SRB). Microbes enriched from groundwater taken from the Test Area North (TAN) site at the Idaho National Engineering and Environmental Laboratory (INEEL) were able to reduce the U(VI) in the adsorption medium as well as the iron on quartz surfaces. Early in the experiment disappearance of U(VI) from solution was a function of chemical interactions since no microbial activity was evident. Abiotic removal of U(VI) was enhanced in the presence of carbonate. As the experiment proceeded, further removal of U(VI) from solution was associated with the fermentation of lactate to propionate and acetate. During later phases of the experiment when lactate was depleted from the growth medium in the microcosm containing the DIRB enrichments, U(VI) concentrations in the solution phase increased until additional lactate was added. When lactate fermentation proceeded, U(VI) concentrations in the liquid phase again returned to near zero. Similar results were shown for the SRB enrichment but less uranium was released back into solution, while in the enrichment with carbonate uranium was not released back into solution. Chemical and biological interactions appear to be important on the mobilization/immobilization of U(VI) in an iron oxide system when TCE is present as a co-contaminant. Interestingly, TCE present in the microcosm experiments was not dechlorinated which was probably an effect of redox conditions that were unsuitable for reductive dechlorination by the microbial culture tested.

  5. Microbially-mediated thiocyanate oxidation and manganese cycling control arsenic mobility in groundwater at an Australian gold mine

    NASA Astrophysics Data System (ADS)

    Horvath, A. S.; Baldisimo, J. G.; Moreau, J. W.

    2010-12-01

    Arsenic contamination of groundwater poses a serious environmental and human health problem in many regions around the world. Historical groundwater chemistry data for a Western-Central Victorian gold mine (Australia) revealed a strong inverse correlation between dissolved thiocyanate and iron(II), supporting the interpretation that oxidation of thiocyanate, a major groundwater contaminant by-product of cyanide-based gold leaching, was coupled to reductive dissolution of iron ox(yhydrox)ides in tailings dam sediments. Microbial growth was observed in this study in a selective medium using SCN- as the sole carbon and nitrogen source. The potential for use of SCN- as a tracer of mining contamination in groundwater was evaluated in the context of biological SCN- oxidation potential in the aquifer. Geochemical data also revealed a high positive correlation between dissolved arsenic and manganese, indicating that sorption on manganese-oxides most likely controls arsenic mobility at this site. Samples of groundwater and sediments along a roughly straight SW-NE traverse away from a large mine tailings storage facility, and parallel to the major groundwater flow direction, were analysed for major ions and trace metals. Groundwater from wells approaching the tailings along this traverse showed a nearly five-fold increase (roughly 25-125 ppb) in dissolved arsenic concentrations relative to aqueous Mn(II) concentrations. Thus, equivalent amounts of dissolved manganese released a five-fold difference in the amount of adsorbed arsenic. The interpretation that reductive dissolution of As-bearing MnO2 at the mine site has been mediated by groundwater (or aquifer) microorganisms is consistent with our recovery of synthetic birnessite-reducing enrichment cultures that were inoculated with As-contaminated groundwaters.

  6. Multi-functional porous mix-valent manganese oxide nano-materials and ruthenium/titanium dioxide for magnetic, electronic, and catalytic applications

    NASA Astrophysics Data System (ADS)

    Shen, Xiongfei

    This thesis contains two parts: (1) development of porous mixed-valent manganese oxide octahedral molecular sieve (OMS) nano-materials with controlled tunnel structures and muilt-functionalities and (2) application of H 2 adsorption for metal particle size evaluation on TiO2 supported Ru Fischer-Tropsch catalysts. Manganese oxide OMS with different nano-scale tunnel sizes may result in various microporosities for different selective catalysis and separation applications. A hydrothermal method was developed to synthesize manganese oxide nano-materials with controlled nano-scale tunnel sizes by hydrothermal treatments of layered structure manganese oxides under different pH conditions. Manganese oxides with increasing tunnel sizes of 2.3 A x 2.3 A (1x1 tunnel structure), 4.6 A x 6.9 A (2x3 tunnel structure), and 4.6 A x 9.2 A (2x4 tunnel structure) were synthesized with increasing pH value from 1.0, 7.0, to 13.0, respectively. Phase transformation mechanism of layered precursors to tunnel structures was obtained by characterization of the materials during synthesis using in situ synchrotron X-ray diffraction. The obtained phase transformation mechanism was used for synthesis of better materials such as new lxl/1x2 tunnel structures and controlled BET surface areas. Most manganese oxide OMS materials show paramagnetism at temperatures from 100 to 350 K. A new method was established to measure the average oxidation state (AOS) of mix-valent manganese in OMS materials by describing their paramagnetic behavior using the Curie-Weiss law. Measurement results show a maximum 7% deviation error compared to the reference titration method for 10 different samples. Magnetism of OMS was further explored by doping Fe into KOMS-2 (a 2x2 tunnel structure manganese oxide) to create high temperature ferromagnetism. The possession of both semiconducting and high temperature ferromagnetism in the Fe-doped KOMS-2 created a highly promising new group of functional materials for spintronics applications. In the second part, effects of temperatures, H2 pressures and adsorption equilibration times on H2 adsorption on Ru/TiO 2 were investigated. By assuming that exposed Ru atoms equally contribute to the three low index planes with the highest atomic density [(001), (100), and (110) planes], the average Ru particle size calculated from monolayer H2 chemisorption (4.6 nm) showed good agreement with the TEM measurement results (4.1 nm).

  7. QUILF: A pascal program to assess equilibria among Fe?Mg?Mn?Ti oxides, pyroxenes, olivine, and quartz

    NASA Astrophysics Data System (ADS)

    Andersen, David J.; Lindsley, Donald H.; Davidson, Paula M.

    1993-10-01

    Program QUILF assesses equilibria among Ti-magnetite, ilmenite, augite, pigeonite, orthopyroxene, olivine, and quartz (or subassemblages thereof). Oxide and silicate equilibria are related through the QUIIF equilibrium: ?Depending on the assemblage, QUILF can provide information on temperature, pressure, oxygen fugacity, and the activities of SiO 2, TiO 2, and Fe o at which the phases were last in equilibrium. For many low-variance assemblages, the system is overdetermined; thus quantitative information can be extracted even if one phase is altered or has reequilibrated. QUILF equilibria can reduce the uncertainties in temperature and oxygen fugacity as determined from coexisting ilmenite and Ti-magnetite alone. QUILF is written in Turbo Pascal for IBM PC and compatibles. The compiled program is approximately 210 kbyte; it also requires two data files that total approximately 10 kbyte. The compositions of the phases first must be projected into seven-component space (CaO?MgO?MnO?FeO?Fe 2O 3TiO 2?SiO 2) before they are used in program QUILF; routines to accomplish this are included in the program, and also are available as separate BASIC programs.

  8. Structural study of biotic and abiotic poorly-crystalline manganese oxides using atomic pair distribution function analysis

    SciTech Connect

    Zhu, Mengqiang; Farrow, Christopher L.; Post, Jeffrey E.; Livi, Kenneth J.T.; Billinge, Simon J.L.; Ginder-Vogel, Matthew; Sparks, Donald L. (Delaware); (Columbia); (JHU); (Smithsonian)

    2012-03-15

    Manganese (Mn) oxides are among the most reactive natural minerals and play an important role in elemental cycling in oceanic and terrestrial environments. A large portion of naturally-occurring Mn oxides tend to be poorly-crystalline and/or nanocrystalline, with not fully resolved crystal structures. In this study, the crystal structures of their synthetic analogs including acid birnessite (AcidBir), {delta}-MnO{sub 2}, polymeric MnO{sub 2} (PolyMnO{sub 2}) and a bacteriogenic Mn oxide (BioMnO{sub x}), have been revealed using atomic pair distribution function (PDF) analysis. Results unambiguously verify that these Mn oxides are layered materials. The best models that accurately allow simulation of pair distribution functions (PDFs) belong to the monoclinic C12/m1 space group with a disk-like shape. The single MnO{sub 6} layers in the average structures deviate significantly from hexagonal symmetry, in contrast to the results of previous studies based on X-ray diffraction analysis in reciprocal space. Manganese occupancies in MnO{sub 6} layers are estimated to be 0.936, 0.847, 0.930 and 0.935, for AcidBir, BioMnOx, {delta}-MnO{sub 2} and PolyMnO{sub 2}, respectively; however, occupancies of interlayer cations and water molecules cannot be accurately determined using the models in this study. The coherent scattering domains (CSDs) of PolyMnO{sub 2}, {delta}-MnO{sub 2} and BioMnO{sub x} are at the nanometer scale, comprising one to three MnO{sub 6} layers stacked with a high disorder in the crystallographic c-axis direction. Overall, the results of this study advance our understanding of the mineralogy of Mn oxide minerals in the environment.

  9. Structural Study of Biotic and Abiotic Poorly-crystalline Manganese Oxides Using Atomic Pair Distribution Function Analysis

    SciTech Connect

    Billinge S. J.; Zhu, M.; Farrow, C.L.; Post, J.E.; Livi, K.J.T.; Ginder-Vogel, M.; Sparks, D.L.

    2012-03-15

    Manganese (Mn) oxides are among the most reactive natural minerals and play an important role in elemental cycling in oceanic and terrestrial environments. A large portion of naturally-occurring Mn oxides tend to be poorly-crystalline and/or nanocrystalline, with not fully resolved crystal structures. In this study, the crystal structures of their synthetic analogs including acid birnessite (AcidBir), {delta}-MnO{sub 2}, polymeric MnO{sub 2} (PolyMnO{sub 2}) and a bacteriogenic Mn oxide (BioMnO{sub x}), have been revealed using atomic pair distribution function (PDF) analysis. Results unambiguously verify that these Mn oxides are layered materials. The best models that accurately allow simulation of pair distribution functions (PDFs) belong to the monoclinic C12/m1 space group with a disk-like shape. The single MnO{sub 6} layers in the average structures deviate significantly from hexagonal symmetry, in contrast to the results of previous studies based on X-ray diffraction analysis in reciprocal space. Manganese occupancies in MnO{sub 6} layers are estimated to be 0.936, 0.847, 0.930 and 0.935, for AcidBir, BioMnO{sub x}, {delta}-MnO{sub 2} and PolyMnO{sub 2}, respectively; however, occupancies of interlayer cations and water molecules cannot be accurately determined using the models in this study. The coherent scattering domains (CSDs) of PolyMnO{sub 2}, {delta}-MnO{sub 2} and BioMnO{sub x} are at the nanometer scale, comprising one to three MnO{sub 6} layers stacked with a high disorder in the crystallographic c-axis direction. Overall, the results of this study advance our understanding of the mineralogy of Mn oxide minerals in the environment.

  10. Graphene-Based Hybrids with Manganese Oxide Polymorphs as Tailored Interfaces for Electrochemical Energy Storage: Synthesis, Processing, and Properties

    NASA Astrophysics Data System (ADS)

    Gupta, S.; van Meveren, M. M.; Jasinski, J.

    2015-01-01

    Technological progress is determined to a greater extent by developments of novel materials or new combinations of known materials with different dimensionality and diverse functionality. In this work, we report on the synthesis and characterization of graphene-based hybrid nanomaterials coupled with transition-metal oxide polymorphs (nano/micro-manganese oxides, i.e., ?-MnO2 [Mn(IV)] and Mn3O4 [Mn(II, III)]). This lays the groundwork for high-performance electrochemical electrodes for alternative energy devices owing to their higher specific capacitance, wide operational potential window and stability through charge-discharge cycling, environmentally benignity, cost-effectiveness, easy processing, and reproducibility on a larger scale. To accomplish this, we strategically designed these hybrids by direct anchoring or physical adsorption of ?-MnO2 and Mn3O4 on variants of graphene, namely graphene oxide and its reduced form, via mixing dispersions of the constituents under mild ultrasonication and drop-casting, resulting in four different combinations. This facile approach affords strong chemical/physical attachment and is expected to result in coupling between the pseudocapacitive transition-metal oxides and supercapacitive nanocarbons showing enhanced activity/reactivity and reasonable areal density of tailored interfaces. We used a range of complementary analytical characterization tools to determine the structure and physical properties, such as scanning electron microscopy combined with energy-dispersive x-ray spectroscopy, atomic force microscopy, x-ray diffraction, resonance Raman spectroscopy combined with elemental Raman mapping, and transmission electron microscopy in conjunction with selected-area electron diffraction. All of these techniques reveal surface morphology, local (lattice dynamical) and average structure, and local charge transfer due to the physically (or chemically) adsorbed manganese oxide of synthesized hybrids that helps to establish microscopic structure-property-function correlations highlighting the surface structure and interfaces to further investigate their electrochemical supercapacitor properties.

  11. Electromagnetic characteristics of manganese oxide-coated Fe3O4 nanoparticles at 2-18 GHz

    NASA Astrophysics Data System (ADS)

    Yang, R. B.; Liang, W. F.; Lin, C. K.

    2011-04-01

    The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the transmission/reflection method in 2-18 GHz. MnOx-coated Fe3O4 NPs were prepared by sol-gel method followed by heat-treating at 300, 400, and 500 °C, respectively. The heat-treated powders were then used as magnetic fillers and added to an epoxy resin to prepare MnOx-coated Fe3O4 composites for the complex permittivity (?'-j??) and permeability (?'-j??) measurements. After the sol-gel process, the coating of manganese oxide (mixture of major Mn2O3 and minor Mn3O4) reduced the value of ?'. The lower the heat-treating temperature, the larger the decrease in ?'. The relative decrease in ?', compared with uncoated Fe3O4 nanoparticles, is 28.7, 23.5, and 20.0% for coated MnOx heat-treated at 300, 400, and 500 °C, respectively, while the relative decrease in ?? is 74.1, 68.8, and 65.2%, respectively. In the present study, MnOx-coated Fe3O4 exhibited a significant decrease in dielectric loss tangent of ˜100% compared to that of uncoated NPs and can be of practical use for microwave components.

  12. Oxidant Selection for the Treatment of Manganese (II), Iron (II), and Arsenic (III) in Groundwaters

    EPA Science Inventory

    In order to comply with the United States Environmental Protection Agency?s (U.S. EPA?s) arsenic standard and the manganese and iron secondary maximum contaminant levels (MCLs) in water (10µg/L, 50µg/L, and 300µg/L, respectively), many Midwestern water utilities must add a strong...

  13. Chromium(III) oxidation by three poorly-crystalline manganese(IV) oxides. 1. Chromium(III)-oxidizing capacity.

    PubMed

    Landrot, Gautier; Ginder-Vogel, Matthew; Livi, Kenneth; Fitts, Jeffrey P; Sparks, Donald L

    2012-11-01

    The Cr(III)-oxidizing capacity of three layered poorly crystalline Mn(IV)O(2) phases, i.e. ?-MnO(2), Random Stacked Birnessite (RSB), and Acid Birnessite (AB), was determined in real-time and in situ, using Quick X-ray Absorption Fine Structure Spectroscopy (Q-XAFS). The results obtained with this technique, which allows the measurement of the total amount of Cr(VI) produced in the system, indicated that the Cr(III) oxidation reaction had ceased between 30 min and 1 h under most experimental conditions. However, this cessation was not observed with a traditional batch technique, which only allows the measurement of Cr(VI) present in solution and thus neglects the amount of Cr(VI) that may be sorbed to Mn(IV)O(2). This study also demonstrated that the Mn(IV)O(2) phase oxidizing the highest amount of Cr(III), which is positively charged in solution, was the mineral featuring the most negatively charged surface. Also, the results indicated that the presence of Mn(II) and/or Mn(III) impurities inside the Mn(IV)O(2) structure could enhance the mineral's capacity to oxidize Cr(III). The information provided in this study will be useful in predicting the capabilities of naturally occurring Mn oxide minerals, which are similar to the three synthetic Mn(IV)O(2) investigated, to oxidize Cr(III) to toxic and mobile Cr(VI) in the soil of contaminated sites. PMID:23050871

  14. Manganese, Metallogenium, and Martian Microfossils

    NASA Technical Reports Server (NTRS)

    Stein, L. Y.; Nealson, K. H.

    1999-01-01

    Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

  15. Bioaccumulation of manganese and its toxicity in feral pigeons (Columba livia) exposed to manganese oxide dust (Mn{sub 3}O{sub 4})

    SciTech Connect

    Sierra, P.; Chakrabarti, S.; Tounkara, R.; Loranger, S.; Kennedy, G.; Zayed, J. [Univ. of Montreal (Canada)] [Univ. of Montreal (Canada)

    1998-11-01

    Manganese tetroxide (Mn{sub 3}O{sub 4}) is a product from the combustion of methylcyclopentadienyl manganese tricarbonyl. Exposure to high levels of manganese can lead to serious health effects especially to the central nervous and respiratory systems. Very few studies on the effects of long-term low level exposure to Mn{sub 3}O{sub 4} have been reported. The present study was therefore conducted to examine the bioaccumulation and toxicity of manganese in various organs of feral pigeons (Columba kivia) when exposed to low levels of Mn{sub 3}O{sub 4} via inhalation and hence to find any possible relationship between these two parameters. A total of 22 pigeons was exposed to 239 {micro}g/m{sup 3} of manganese for 7 h/day, 5 days/week for 5, 9, and 13 consecutive weeks. Manganese concentrations in various tissues, e.g., brain (mesencephalon), lung, liver, intestine, pancreas, kidney, muscle, bone, and whole blood, were measured by neutron activation analysis. Various biochemical parameters in blood, e.g., hematocrit, total proteins, glucose, uric acid, alinine aminotransferase, total iron, blood urea nitrogen and triglycerides, were also measured.

  16. Chemical and microbiological studies of sulfide?mediated manganese reduction

    Microsoft Academic Search

    David J. Burdige; Kenneth H. Nealson

    1986-01-01

    Laboratory studies of manganese reduction by naturally occurring reduced inorganic compounds were undertaken, both to study further possible in situ mechanisms of manganese reduction and to examine how manganese redox reactions might be coupled to other biogeochemical processes. Chemical manganese reduction by sulfide (in the presence of excess manganese oxide) was found to be rapid and complete, with all sulfide

  17. Modeling the adsorption of mercury(II) on (hydr)oxides. 1: Amorphous iron oxide and {alpha}-quartz

    SciTech Connect

    Tiffreau, C.; Luetzenkirchen, J.; Behra, P. [Univ. Louis Pasteur, Strasbourg (France). Inst. de Mecanique des Fluides] [Univ. Louis Pasteur, Strasbourg (France). Inst. de Mecanique des Fluides

    1995-06-01

    In this study, the authors provide a single model capable of describing the behavior of mercury(II) at two different solid/water interfaces. Mercury(II) sorption on amorphous ferric oxide (HFO) and {alpha}-SiO{sub 2} can be simulated using the surface complexation approach. In both cases, experiments are best reproduced when ternary surface complexes between the surface ({triple_bond}S-OH{sup 0}), Hg{sup 2+}, OH{sup {minus}} or Cl{sup {minus}} are included in the model. Sorption of ternary surface complexes predominates in the case of {alpha}-SiO{sub 2}. In addition, in the case of HFO, additional precipitation reactions of a nonideal Hg(OH){sub 2}-Fe(OH){sub 3} solid solution are needed at high sorbate to sorbent ratios. The modeling leads to a new set of surface complexation constants for the interaction between Hg{sup 2+} and these oxide surfaces which are described herein.

  18. Structural Study of Poorly Crystalline Layered Manganese Oxides Using the Atomic Pair Distribution Function Technique. Tuesday, November 3, 2009: 11:15 AM

    E-print Network

    Sparks, Donald L.

    Structural Study of Poorly Crystalline Layered Manganese Oxides Using the Atomic Pair Distribution. of Delaware, Bear, DE (4)Univ. of Delaware, Newark, DE The atomic pair distribution function (PDF) is a powerful technique to analyze crystal structures of nanoparticulate, poorly crystalline and amorphous

  19. The impact of partial manganese superoxide dismutase (SOD2)-deficiency on mitochondrial oxidant stress, DNA fragmentation and liver injury during acetaminophen hepatotoxicity

    Microsoft Academic Search

    Anup Ramachandran; Margitta Lebofsky; Steven A. Weinman; Hartmut Jaeschke

    2011-01-01

    Acetaminophen (APAP) hepatotoxicity is the most frequent cause of acute liver failure in many countries. The mechanism of cell death is initiated by formation of a reactive metabolite that binds to mitochondrial proteins and promotes mitochondrial dysfunction and oxidant stress. Manganese superoxide dismutase (SOD2) is a critical defense enzyme located in the mitochondrial matrix. The objective of this investigation was

  20. The Influence of the Local Lattice Distortion and Magnetic Ordering in Manganese Oxides on the Mn and O K-XANES

    SciTech Connect

    Krayzman, Victor; Maznichenko, Igor; Novakovich, Alexander; Vedrinskii, Rostislav [Rostov State University, 5 Zorge Str. Rostov-on-Don, 344090 (Russian Federation)

    2007-02-02

    Calculations of Mn and O K-XANES in perovskite-like structure manganese oxides performed by the full multiple scattering method within the spin-dependent exchange potential model enable to determine local lattice distortions and demonstrate the effect of the crystal magnetic order on the near-edge structure.

  1. X-ray absorption investigation on the ternary system lithium manganese oxide

    Microsoft Academic Search

    T Buhrmester; M Martin

    2000-01-01

    In this paper we show that the lithium manganese spinel, Li1+xMn2O4 with lithium excess up to x=0.2 can be prepared using the Pechini-method which starts off with aqueous solutions of nitrates. The characterization of the samples by AAS and X-ray diffraction exhibits single phase material. X-ray absorption (XAS) experiments at the Mn–K edge lead to the conclusion that spinel with

  2. Carbamazepine oxidation catalyzed by iron and manganese porphyrins supported on aminofunctionalized matrices

    Microsoft Academic Search

    André L. Faria; Tatiana C. O. Mac Leod; Marilda D. Assis

    2008-01-01

    This work describes the catalytic activity of manganese and iron porphyrins, Mn and Fe(TFPP)Cl, covalently immobilized on the aminofunctionalized supports montmorillonite K-10 (MontX) and silica (SilX), where X=1 or 2 represents the length of the organic chain (“arms”) binding the metalloporphyrin to the support. These systems were characterized by UV–vis and Electronic Paramagnetic Resonance (EPR), and they were used as

  3. Heteroepitaxial Nucleation and Oriented Growth of Manganese

    E-print Network

    Heteroepitaxial Nucleation and Oriented Growth of Manganese Oxide Islands on Carbonate Minerals and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 Manganese redox cycling study, Mn2+(aq) is reacted with O2(aq) at circumneutral pH to form manganese oxide islands on the (101h4

  4. Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors

    NASA Astrophysics Data System (ADS)

    Puranen, Jouni; Laakso, Jarmo; Kylmälahti, Mikko; Vuoristo, Petri

    2013-06-01

    A modified high-velocity oxy-fuel spray (HVOF) thermal spray torch equipped with liquid feeding hardware was used to spray manganese-cobalt solutions on ferritic stainless steel grade Crofer 22 APU substrates. The HVOF torch was modified in such a way that the solution could be fed axially into the combustion chamber through 250- and 300-?m-diameter liquid injector nozzles. The solution used in this study was prepared by diluting nitrates of manganese and cobalt, i.e., Mn(NO3)2·4H2O and Co(NO3)2·6H2O, respectively, in deionized water. The as-sprayed coatings were characterized by X-ray diffraction and field-emission scanning electron microscopy operating in secondary electron mode. Chemical analyses were performed on an energy dispersive spectrometer. Coatings with remarkable density could be prepared by the novel high-velocity solution precursor flame spray (HVSPFS) process. Due to finely sized droplet formation in the HVSPFS process and the use of as delivered Crofer 22 APU substrate material having very low substrate roughness ( R a < 0.5 ?m), thin and homogeneous coatings, with thicknesses lower than 10 ?m could be prepared. The coatings were found to have a crystalline structure equivalent to MnCo2O4 spinel with addition of Co-oxide phases. Crystallographic structure was restored back to single-phase spinel structure by heat treatment.

  5. Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles

    PubMed Central

    2012-01-01

    In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies. PMID:22296968

  6. First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries.

    PubMed

    Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François; Bourbon, Carole; Patoux, Sébastien

    2013-08-14

    Lithium-rich manganese-based layered oxides Li[Li(x)Mn(y)TM(1-x-y)]O2 with TM standing for Ni, Co, or Fe are of great interest as cathode materials for lithium ion batteries. Indeed, among all of the materials, they offer the highest rechargeable capacity and energy density. However, when used, they suffer from complex evolutions that need to be understood before their practical use. Here we report on such evolutions studied using advanced transmission electron microscopy. Structural modifications are directly observed at the atomic scale using Cs corrected STEM HAADF imaging technique, and the chemical modifications are probed by the means of STEM EELS experiments. For the first time, segregation between nickel and manganese close the particle surface is pointed out. Finally, observed evolutions are correlated within a proposed mechanism that leads to the densification of the material. Our results allow understanding the link between the decrease of electrochemical performance and these evolutions occurring into the material upon cycling. PMID:23876058

  7. Chemical versus Enzymatic Digestion of Contaminated Estuarine Sediment: Relative Importance of Iron and Manganese Oxides in Controlling Trace Metal Bioavailability

    NASA Astrophysics Data System (ADS)

    Turner, A.; Olsen, Y. S.

    2000-12-01

    Chemical and enzymatic reagents have been employed to determine available concentrations of Fe, Mn, Cu and Zn in contaminated estuarine sediment. Gastric and intestinal enzymes (pepsin, pH 2, and trypsin, pH 7·6, respectively) removed significantly more metal than was water-soluble or exchangeable (by seawater or ammonium acetate), while gastro-intestinal fluid of the demersal teleost, Pleuronectes platessa L. (plaice), employed to operationally define a bioavailable fraction of contaminants, generally solubilized more metal than the model enzymes. Manganese was considerably more available than Fe under these conditions and it is suggested that the principal mechanism of contaminant release is via surface complexation and reductive solubilization of Mn oxides, a process which is enhanced under conditions of low pH. Of the chemical reagents tested, acetic acid best represents the fraction of Mn (as well as Cu and Zn) which is available under gastro-intestinal conditions, suggesting that the reducing tendency of acetate is similar to that of the ligands encountered in the natural digestive environment. Although the precise enzymatic and non-enzymatic composition of plaice gastro-intestinal fluid may be different to that encountered in more representative, filter-feeding or burrowing organisms, a general implication of this study is that contaminants associated with Mn oxides are significantly more bioavailable than those associated with Fe oxides, and that contaminant bioavailability may be largely dictated by the oxidic composition of contaminated sediment.

  8. Kinetics of chromium(III) oxidation by manganese(IV) oxides using quick scanning X-ray absorption fine structure spectroscopy (Q-XAFS).

    PubMed

    Landrot, Gautier; Ginder-Vogel, Matthew; Sparks, Donald L

    2010-01-01

    The initial kinetics of Cr(III) oxidation on mineral surfaces is poorly understood, yet a significant portion of the oxidation process occurs during the first seconds of reaction. In this study, the initial rates of Cr(III) oxidation on hydrous manganese oxide (HMO) were measured at three different pH values (pH 2.5, 3, and 3.5), using a quick X-ray absorption fine structure spectroscopy (Q-XAFS) batch method. The calculated rate constants were 0.201, 0.242, and 0.322 s(-1) at pH 2.5, 3, and 3.5, respectively. These values were independent of both [Cr(III)] and [Mn(II)] and mixing speed, suggesting that the reaction was "chemically" controlled and not dependent upon diffusion at the time period the rate parameters were measured. A second-order overall rate was found at three pH values. This represents the first study to determine the chemical kinetics of Cr(III) oxidation on Mn-oxides. The results have important implications for the determination of rapid, environmentally important reactions that cannot be measured with traditional batch and flow techniques. An understanding of these reactions is critical to predicting the fate of contaminants in aquatic and terrestrial environments. PMID:19950944

  9. A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries.

    PubMed

    Guo, Shaohua; Yu, Haijun; Jian, Zelang; Liu, Pan; Zhu, Yanbei; Guo, Xianwei; Chen, Mingwei; Ishida, Masayoshi; Zhou, Haoshen

    2014-08-01

    A layered sodium manganese oxide material (NaMn3 O5 ) is introduced as a novel cathode materials for sodium-ion batteries. Structural characterizations reveal a typical Birnessite structure with lamellar stacking of the synthetic nanosheets. Electrochemical tests reveal a particularly large discharge capacity of 219 mAh g(-1) in the voltage rang of 1.5-4.7 V vs. Na/Na(+) . With an average potential of 2.75 V versus sodium metal, layered NaMn3 O5 exhibits a high energy density of 602 Wh kg(-1) , and also presents good rate capability. Furthermore, the diffusion coefficient of sodium ions in the layered NaMn3 O5 electrode is investigated by using the galvanostatic intermittent titration technique. The results greatly contribute to the development of room-temperature sodium-ion batteries based on earth-abundant elements. PMID:24919424

  10. Design, synthesis, and characterization of materials for controlled line deposition, environmental remediation, and doping of porous manganese oxide material

    NASA Astrophysics Data System (ADS)

    Calvert, Craig A.

    This thesis covers three topics: (1) coatings formed from sol-gel phases, (2) environmental remediation, and (3) doping of a porous manganese oxide. Synthesis, characterization, and application were investigated for each topic. Line-formations were formed spontaneously by self-assembly from vanadium sol-gels and other metal containing solutions on glass substrates. The solutions were prepared by the dissolution of metal oxide or salt in water. A more straightforward method is proposed than used in previous work. Analyses using optical microscopy, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and infrared spectroscopy showed discreet lines whose deposition could be controlled by varying the concentration. A mechanism was developed from the observed results. Microwave heating, the addition of graphite rods, and oxidants, can enhance HCB remediation from soil. To achieve remediation, a TeflonRTM vessel open to the atmosphere along with an oxidant, potassium persulfate (PerS) or potassium hydroxide, along with uncoated or aluminum oxide coated, graphite rods were heated in a research grade microwave oven. Microwave heating was used to decrease the heating time, and graphite rods were used to increase the absorption of the microwave energy by providing thermal centers. The results showed that the percent HCB removed was increased by adding graphite rods and oxidants. Tungsten, silver, and sulfur were investigated as doping agents for K--OMS-2. The synthesis of these materials was carried out with a reflux method. The doping of K--OMS-2 led to changes in the properties of a tungsten doped K--OMS-2 had an increased resistivity, the silver doped material showed improved epoxidation of trans-stilbene, and the addition of sulfur produced a paper-like material. Rietveld refinement of the tungsten doped K--OMS-2 showed that the tungsten was doped into the framework.

  11. Anthocyanin-rich açaí (Euterpe oleracea Mart.) extract attenuates manganese-induced oxidative stress in rat primary astrocyte cultures.

    PubMed

    da Silva Santos, Vivian; Bisen-Hersh, Emily; Yu, Yingchun; Cabral, Ingridy Simone Ribeiro; Nardini, Viviani; Culbreth, Megan; Teixeira da Rocha, João Batista; Barbosa, Fernando; Aschner, Michael

    2014-01-01

    Manganese (Mn) is an essential element for human health. However, at high concentrations Mn may be neurotoxic. Mn accumulates in astrocytes, affecting their redox status. In view of the high antioxidant and anti-inflammatory properties of the exotic Brazilian fruit açaí (Euterpe oleracea Mart.), its methanolic extract was obtained by solid-phase extraction (SPE). This açaí extract showed considerable anthocyanins content and direct antioxidant capacity. The açaí extract scavenged 2,2-diphenyl-1-picrylhydrazyl radicals (DPPH•) with an EC?? of 19.1 ppm, showing higher antioxidant activity compared to butylated hydroxytoluene (BHT), but lower than ascorbic acid and quercetin. This obtained açaí extract also attenuated Mn-induced oxidative stress in primary cultured astrocytes. Specifically, the açaí extract at an optimal and nutritionally relevant concentration of 0.1 ?g/ml prevented Mn-induced oxidative stress by (1) restoring GSH/GSSG ratio and net glutamate uptake, (2) protecting astrocytic membranes from lipid peroxidation, and (3) decreasing Mn-induced expression of erythroid 2-related factor (Nrf2) protein. A larger quantity of açaí extract exacerbated the effects of Mn on these parameters except with respect to lipid peroxidation assessed by means of F?-isoprostanes. These studies indicate that at nutritionally relevant concentration, anthocyanins obtained from açaí protect astrocytes against Mn neurotoxicity, but at high concentrations, the "pro-oxidant" effects of its constituents likely prevail. Future studies may be profitably directed at potential protective effects of açaí anthocyanins in nutraceutical formulations. PMID:24617543

  12. Oxidative aliphatic C-H fluorination with manganese catalysts and fluoride ion.

    PubMed

    Liu, Wei; Huang, Xiongyi; Groves, John T

    2013-12-01

    Fluorination is a reaction that is useful in improving the chemical stability and changing the binding affinity of biologically active compounds. The protocol described here can be used to replace aliphatic, C(sp(3))-H hydrogen in small molecules with fluorine. Notably, isolated methylene groups and unactivated benzylic sites are accessible. The method uses readily available manganese porphyrin and manganese salen catalysts and various fluoride ion reagents, including silver fluoride (AgF), tetrabutylammonium fluoride and triethylamine trihydrofluoride (TREAT·HF), as the source of fluorine. Typically, the reactions afford 50-70% yield of mono-fluorinated products in one step. Two representative examples, the fragrance component celestolide and the nonsteroidal anti-inflammatory drug ibuprofen, are described; they produced useful isolated quantities (250-300 mg, ~50% yield) of fluorinated material over periods of 1-8 h. The procedures are performed in a typical fume hood using ordinary laboratory glassware. No special precautions to rigorously exclude water are required. PMID:24177292

  13. Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 1, aging mechanisms and life estimation

    NASA Astrophysics Data System (ADS)

    Wang, John; Purewal, Justin; Liu, Ping; Hicks-Garner, Jocelyn; Soukazian, Souren; Sherman, Elena; Sorenson, Adam; Vu, Luan; Tataria, Harshad; Verbrugge, Mark W.

    2014-12-01

    We examine the aging and degradation of graphite/composite metal oxide cells. Non-destructive electrochemical methods were used to monitor the capacity loss, voltage drop, resistance increase, lithium loss, and active material loss during the life testing. The cycle life results indicated that the capacity loss was strongly impacted by the rate, temperature, and depth of discharge (DOD). Lithium loss and active electrode material loss were studied by the differential voltage method; we find that lithium loss outpaces active material loss. A semi-empirical life model was established to account for both calendar-life loss and cycle-life loss. For the calendar-life equation, we adopt a square root of time relation to account for the diffusion limited capacity loss, and an Arrhenius correlation is used to capture the influence of temperature. For the cycle life, the dependence on rate is exponential while that for time (or charge throughput) is linear.

  14. Degradation of aqueous and soil-sorbed estradiol using a new class of stabilized manganese oxide nanoparticles.

    PubMed

    Han, Bing; Zhang, Man; Zhao, Dongye; Feng, Yucheng

    2015-03-01

    Manganese oxide (MnO2) was reported to be effective for degrading aqueous pharmaceutical chemicals. However, little is known about its potential use for degrading soil-sorbed contaminants. To bridge this knowledge gap, we synthesized, for the first time, a class of stabilized MnO2 nanoparticles using carboxymethyl celluloses (CMC) as a stabilizer, and tested their effectiveness for degrading aqueous and soil-sorbed estradiol. The most desired particles (highest reactivity and soil deliverability) were obtained at a CMC/MnO2 molar ratio of 1.39 × 10(-3), which yielded a mean hydrodynamic size of 39.5 nm and a narrow size distribution (SD = 0.8 nm). While non-stabilized MnO2 particles rapidly aggregated and were not transportable through a soil column, CMC-stabilized nanoparticles remained fully dispersed in water and were soil deliverable. At typical aquatic pH (6-7), CMC-stabilized MnO2 exhibited faster degradation kinetics for oxidation of 17?-estradiol than non-stabilized MnO2. The reactivity advantage becomes more evident when used for treating soil-sorbed estradiol owing to the ability of CMC to complex with metal ions and prevent the reactive sites from binding with inhibitive soil components. A retarded first-order rate model was able to interpret the oxidation kinetics for CMC-stabilized MnO2. When used for degrading soil-sorbed estradiol, several factors may inhibit the oxidation effectiveness, including desorption rate, soil-MnO2 interactions, and soil-released metals and reductants. CMC-stabilized MnO2 nanoparticles hold the potential for facilitating in situ oxidative degradation of various emerging contaminants in soil and groundwater. PMID:25543239

  15. Daily Manganese Intake Status and Its Relationship with Oxidative Stress Biomarkers under Different Body Mass Index Categories in Korean Adults

    PubMed Central

    Bu, So-Young

    2012-01-01

    Manganese (Mn) is an essential micronutrient for human and plays an important role as a cofactor for several enzymes involving fatty acid synthesis, hepatic gluconeogenesis, and oxidative stresses. Also, Mn intake status has been reported to have beneficial effects in reversing metabolic dysfunction including obesity and nonalcoholic steatosis which is linked to mitochondrial dysfunction and oxidative stresses, however, information on dietary Mn intake in Koreans are limited. Hence we investigated the relationship between dietary Mn intake and antioxidant defense factors in healthy and obese subjects. Total of 333 healthy subjects were recruited in the study and were assigned to one of three study groups: a normal group (18.5-22.9), a overweight group (23-24.9), and a obesity group (>25) according to their body mass index (BMI). We assessed Mn intakes (24-hr recall method) and several indicators for antioxidative defenses such as glutathione (GSH), glutathione peroxidase (GPx) and urinary malonaldehyde (MDA). Results showed that body weight and blood pressure of study subjects were increased in dependent of their BMI (p < 0.01). However dietary Mn intakes and oxidative stress biomarkers (GSH, GPx, and MDA) were not significantly different by groups defined by BMI. In correlation analysis adjusting for age, sex and energy intake, dietary Mn intake of the subjects in different BMI categories were not significantly correlated with GSH, GPx, MDA and showed a weak or no association with these oxidative stress markers. In conclusion dietary Mn intake at least in this study has a little or no influence on markers of oxidative status in both healthy and obese subjects. PMID:23431039

  16. Cr(III) Oxidation and Cr Toxicity in Cultures of the Manganese(II)Oxidizing Pseudomonas putida Strain GB1

    Microsoft Academic Search

    Karen J. Murray; Mylene L. Mozafarzadeh; Bradley M. Tebo

    2005-01-01

    Mn oxides have long been considered the primary environmental oxidant of Cr(III), however, since most of the reactive Mn oxides in the environment are believed to be of biological origin, microorganisms may indirectly mediate Cr(III) oxidation and accelerate the rate over that seen in purely abiotic systems. In this study, we examined the ability of the Mn(II)-oxidizing bacterium, Pseudomonas putida

  17. Nanolayered manganese oxide/C(60) composite: a good water-oxidizing catalyst for artificial photosynthetic systems.

    PubMed

    Najafpour, Mohammad Mahdi; Abasi, Mahnaz; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-08-21

    For the first time, we considered Mn oxide/C60 composites as water-oxidizing catalysts. The composites were synthesized by easy and simple procedures, and characterized by some methods. The water-oxidizing activities of these composites were also measured in the presence of cerium(iv) ammonium nitrate. We found that the nanolayered Mn oxide/C60 composites show promising activity toward water oxidation. PMID:24984108

  18. Water oxidation by manganese oxides, a new step towards a complete picture: simplicity is the ultimate sophistication.

    PubMed

    Najafpour, Mohammad Mahdi; Sedigh, Davood Jafarian

    2013-09-14

    We, for the first time, report that many Mn oxides (Mn3O4, ?-Mn2O3, ?-MnO2, CaMnO3, Ca2Mn3O8, CaMn3O6 and CaMn4O8) in the presence of cerium(IV) ammonium nitrate, in the water oxidation, convert to layered Mn oxide. This layered Mn oxide is an efficient water oxidizing catalyst. PMID:23838901

  19. Iron, copper, and manganese complexes with in vitro superoxide dismutase and/or catalase activities that keep Saccharomyces cerevisiae cells alive under severe oxidative stress.

    PubMed

    Ribeiro, Thales P; Fernandes, Christiane; Melo, Karen V; Ferreira, Sarah S; Lessa, Josane A; Franco, Roberto W A; Schenk, Gerhard; Pereira, Marcos D; Horn, Adolfo

    2015-03-01

    Due to their aerobic lifestyle, eukaryotic organisms have evolved different strategies to overcome oxidative stress. The recruitment of some specific metalloenzymes such as superoxide dismutases (SODs) and catalases (CATs) is of great importance for eliminating harmful reactive oxygen species (hydrogen peroxide and superoxide anion). Using the ligand HPClNOL {1-[bis(pyridin-2-ylmethyl)amino]-3-chloropropan-2-ol}, we have synthesized three coordination compounds containing iron(III), copper(II), and manganese(II) ions, which are also present in the active site of the above-noted metalloenzymes. These compounds were evaluated as SOD and CAT mimetics. The manganese and iron compounds showed both SOD and CAT activities, while copper showed only SOD activity. The copper and manganese in vitro SOD activities are very similar (IC50~0.4?mol dm(-3)) and about 70-fold higher than those of iron. The manganese compound showed CAT activity higher than that of the iron species. Analyzing their capacity to protect Saccharomyces cerevisiae cells against oxidative stress (H2O2 and the O2(•-) radical), we observed that all compounds act as antioxidants, increasing the resistance of yeast cells mainly due to a reduction of lipid oxidation. Especially for the iron compound, the data indicate complete protection when wild-type cells were exposed to H2O2 or O2(•-) species. Interestingly, these compounds also compensate for both superoxide dismutase and catalase deficiencies; their antioxidant activity is metal ion dependent, in the order iron(III)>copper(II)>manganese(II). The protection mechanism employed by the complexes proved to be independent of the activation of transcription factors (such as Yap1, Hsf1, Msn2/Msn4) and protein synthesis. There is no direct relation between the in vitro and the in vivo antioxidant activities. PMID:25511255

  20. Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

    SciTech Connect

    Aller, R.C.; Rude, P.D. (State Univ. of New York, Stony Brook (USA))

    1988-03-01

    During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO{sup =}{sub 4} under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn{sup +4} are apparently more effective than Mn{sup +3} in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and Azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly autotrophic CO{sub 2} fixation. Lack of sensitivity to chlorate suggests that a NO{sup {minus}}{sub 3} reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O{sub 2}. Alkalinity is also simultaneously depleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

  1. In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

    PubMed Central

    Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

    2013-01-01

    In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

  2. Synthesis of magnetic core/shell carbon nanosphere supported manganese catalysts for oxidation of organics in water by peroxymonosulfate.

    PubMed

    Wang, Yuxian; Sun, Hongqi; Ang, Ha Ming; Tadé, Moses O; Wang, Shaobin

    2014-11-01

    Magnetic separation is more cost-effective than conventional separation processes in heterogeneous catalysis, especially for ultrafine nanoparticles. Magnetic core/shell nanospheres (MCS, Fe3O4/carbon) were synthesized by a hydrothermal method and their supported manganese oxide nanoparticles (Mn/MCS) were obtained by redox reactions between MCS and potassium permanganate at a low temperature. The materials were analyzed by a variety of characterization techniques such as powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectrometer (EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and N2 adsorption/desorption. The Mn/MCS catalysts were able to effectively activate Oxone® for phenol degradation in aqueous solutions. Nitrogen treated MCS supported Mn achieved 100% conversion within 120min. Kinetic studies showed that phenol degradation over supported Mn catalysts follows the first order kinetics. It was also found that the catalysts can be easily separated from the aqueous solutions by an external magnetic field. The Oxone® activation mechanism by Mn/MCS catalysts was discussed and sulfate radicals were suggested to be the primary reactive species generated from peroxymonosulfate (PMS) for phenol catalytic oxidation. PMID:25112914

  3. The influence of manganese-cobalt oxide/graphene on reducing fire hazards of poly(butylene terephthalate).

    PubMed

    Wang, Dong; Zhang, Qiangjun; Zhou, Keqing; Yang, Wei; Hu, Yuan; Gong, Xinglong

    2014-08-15

    By means of direct nucleation and growth on the surface of graphene and element doping of cobalt oxide (Co3O4) nano-particles, manganese-cobalt oxide/graphene hybrids (MnCo2O4-GNS) were synthesized to reduce fire hazards of poly(butylene terephthalate) (PBT). The structure, elemental composition and morphology of the obtained hybrids were surveyed by X-ray diffraction, X-ray photoelectron spectrometer and transmission electron microscopy, respectively. Thermogravimetric analysis was applied to simulate and study the influence of MnCo2O4-GNS hybrids on thermal degradation of PBT during combustion. The fire hazards of PBT and its composites were assessed by the cone calorimeter. The cone test results had showed that peak HRR and SPR values of MnCo2O4-GNS/PBT composites were lower than that of pure PBT and Co3O4-GNS/PBT composites. Furthermore, the incorporation of MnCo2O4-GNS hybrids gave rise to apparent decrease of pyrolysis products containing aromatic compounds, carbonyl compounds, carbon monoxide and carbon dioxide, attributed to combined impact of physical barrier for graphene and cat O4 for organic volatiles and carbon monoxide. PMID:24997255

  4. Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3

    NASA Astrophysics Data System (ADS)

    Pourkhalil, Mahnaz; Moghaddam, Abdolsamad Zarringhalam; Rashidi, Alimorad; Towfighi, Jafar; Mortazavi, Yadollah

    2013-08-01

    Manganese oxide catalysts (MnOx) supported on functionalized multi-walled carbon nanotubes (FMWNTs) for low temperature selective catalytic reduction (LTSCR) of nitrogen oxides (NOx) with NH3 in the presence of excess O2 were prepared by the incipient wetness impregnation method. These catalysts were characterized by N2 adsorption, Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and H2-temperature programmed reduction (H2-TPR) methods. The effects of reaction temperature, MnOx loading, calcination temperature and calcination time were investigated. The presence of surface nitrate species under moderate calcination conditions may play a favorable role in the LTSCR of NOx with NH3. Under the reaction conditions of 200 °C, 1 bar, NO = NH3 = 900 ppm, O2 = 5 vol%, GHSV = 30,000 h-1 and 12 wt% MnOx, NOx conversion and N2 selectivity were 97% and 99.5%, respectively. The SCR activity was reduced in the presence of 100 ppm SO2 and 2.5 vol% H2O from 97% to 92% within 6 h at 200 °C, however such an effect was shown to be reversible by exposing the catalyst to a helium flow for 2 h at 350 °C due to thermal decomposition of ammonium sulphate salts.

  5. Oxidation Of Manganese At Kimberley, Gale Crater: More Free Oxygen In Mars' Past?

    NASA Technical Reports Server (NTRS)

    Lanza, N. L.; Wiens, R. C.; Arvidson, R. E.; Clark, B. C.; Fischer, W. W.; Gellert, R.; Grotzinger, J. P.; Hurowitz, J. A.; McLennan, S. M.; Morris, R. V.; Rice, M. S.; Bell, J. F., III; Berger, J. A.; Blaney, D. L.; Bridges, N. T.; Calef, F., III; Campbell, J. L.; Clegg, S. M.; Cousin, A.; Edgett, K. S.; Fabre, C.; Fisk, M. R.; Forni, O.; Frydenvang, J.; Ming, D. W.

    2015-01-01

    High Mn concentrations provide unique indicators of water-rich environments and their redox state. Very high-potential oxidants are required to oxidize Mn to insoluble, high-valence oxides that can precipitate and concentrate Mn in rocks and sediments; these redox potentials are much higher than those needed to oxidize Fe or S. Consequently, Mn-rich rocks on Earth closely track the rise of atmospheric oxygen. Given the association between Mn-rich rocks and the redox state of surface environments, observations of anomalous Mn enrichments on Mars raise similar questions about redox history, solubility and aqueous transport, and availability as a metabolic substrate. Our observations suggest that at least some of the high Mn present in Gale crater occurs in the form of Mn-oxides filling veins that crosscut sand-stones, requiring post-depositional precipitation as highly oxidizing fluids moved through the fractured strata after their deposition and lithification.

  6. Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

    Microsoft Academic Search

    R. C. Aller; P. D. Rude

    1988-01-01

    During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO{sup =}â under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn{sup +4}

  7. In situ control of the oxide layer on thermally evaporated titanium and lysozyme adsorption by means of electrochemical quartz crystal microbalance with dissipation.

    PubMed

    Van De Keere, Isabel; Svedhem, Sofia; Högberg, Hans; Vereecken, Jean; Kasemo, Bengt; Hubin, Annick

    2009-02-01

    Electrochemical (EC) quartz crystal microbalance with dissipation monitoring (ECQCM-D) is a new and powerful technique for the in situ study of adsorption phenomena, e.g., as a function of the potential of the substrate. When titanium (Ti) is employed as the substrate, its oxidation behavior needs to be taken into account. Ti is always covered with a native oxide layer that can grow by, e.g., thermal oxidation or under anodic polarization. For biomolecular adsorption studies on oxidized Ti under applied potential, a stable oxide layer is desired in order to be able to distinguish the adsorption phenomena and the oxide growth. Therefore, the oxidation of thermally evaporated Ti films was investigated in phosphate-buffered saline by means of ECQCM-D, using a specially designed EC flow cell. Upon stepping the potential applied to Ti up to 2.6 V vs standard hydrogen electrode (SHE), a fast increase of the mass was observed initially for each potential step, evolving slowly to an asymptotic mass change after several hours. The oxide layer thickness increased as a quasi-linear function of the oxidation potential for potentials up to 1.8 V vs SHE. The growth rate of the oxide was around 2.5-3 nm/V. No changes in the dissipation shift were observed for potentials up to 1.8 V vs SHE. The composition of the oxide layer was analyzed by X-ray photoelectron spectroscopy (XPS). It was mainly composed of TiO(2), with a small percentage of suboxides (TiO and Ti(2)O(3)) primarily at the inner metal/oxide interface. The amount of TiO(2) increased, and that of TiO and Ti(2)O(3) decreased, with increasing oxidation potential. For each oxidation potential, the calculated thickness obtained from ECQCM-D correlated well with the thickness obtained by XPS depth profiling. A procedure to prepare Ti samples with a stable oxide layer was successfully established for investigations on the influence of an electric field on the adsorption of biomolecules. As such, the effect of an applied potential on the adsorption behavior of lysozyme on oxidized Ti was investigated. It was observed that the adsorption of lysozyme on oxidized Ti was not influenced by the applied potential. PMID:20353217

  8. Kinetics and mechanism of benzene oxidation by peroxymonosulfate catalyzed with a binuclear manganese(IV) complex in the presence of oxalic acid

    NASA Astrophysics Data System (ADS)

    Shul'pina, L. S.; Kozlov, Yu. N.; Strelkova, T. V.; Shul'pin, G. B.

    2013-03-01

    It is established that Oxone (peroxymonosulfate, 2KHSO5 · KHSO4 · K2SO4) oxidizes benzene to p-quinone very efficiently and selectively in a homogeneous solution in aqueous acetonitrile in the presence of a catalyst, i.e., dimeric manganese(IV) complex [LMn(O)3MnL](PF6)2 where L is 1,4,7-trimethyl-1,4,7-triazacyclononane, and a cocatalyst, i.e., oxalic acid. The dependences of the maximum rate of quinone accumulation on the initial concentrations of reagents are studied. It is proposed that benzene is oxidized by the manganyl particle containing the Mn(V)=O fragment that forms upon the reaction of the reduced form of the starting dimeric manganese complex with Oxone.

  9. 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 mnxG, suggesting that this MCO directly catalyzes the oxidation of Mn(II) and the precipitation of Mn(IV) oxide, which represents a novel reaction for a MCO. MS/MS analysis of bands identified by in-gel activity assays is a powerful method of identifying novel enzymes responsible for geochemical processes.

  10. Influence of substrate treatment temperatures and bias potential on capacitive manganese–cobalt–zinc oxide thin films deposited by radio frequency sputtering

    Microsoft Academic Search

    Chuen-Chang Lin; Jhang-Hao Jhan

    2011-01-01

    Manganese–cobalt–zinc oxide films are deposited on graphite foils by a dry process, simpler one-step radio frequency sputtering with different substrate treatment temperatures and bias potential. The best long-term operational stability (only reduce about 7% specific capacitance at the 8000th cycle of potential cycling) and good specific capacitance are obtained at a substrate treatment temperature of 200°C and without substrate bias

  11. PerR-regulated manganese ion uptake contributes to oxidative stress defense in an oral streptococcus.

    PubMed

    Wang, Xinhui; Tong, Huichun; Dong, Xiuzhu

    2014-04-01

    Metal homeostasis plays a critical role in antioxidative stress. Streptococcus oligofermentans, an oral commensal facultative anaerobe lacking catalase activity, produces and tolerates abundant H2O2, whereas Dpr (an Fe(2+)-chelating protein)-dependent H2O2 protection does not confer such high tolerance. Here, we report that inactivation of perR, a peroxide-responsive repressor that regulates zinc and iron homeostasis in Gram-positive bacteria, increased the survival of H2O2-pulsed S. oligofermentans 32-fold and elevated cellular manganese 4.5-fold. perR complementation recovered the wild-type phenotype. When grown in 0.1 to 0.25 mM MnCl2, S. oligofermentans increased survival after H2O2 stress 2.5- to 23-fold, and even greater survival was found for the perR mutant, indicating that PerR is involved in Mn(2+)-mediated H2O2 resistance in S. oligofermentans. Mutation of mntA could not be obtained in brain heart infusion (BHI) broth (containing ~0.4 ?M Mn(2+)) unless it was supplemented with ?2.5 ?M MnCl2 and caused 82 to 95% reduction of the cellular Mn(2+) level, while mntABC overexpression increased cellular Mn(2+) 2.1- to 4.5-fold. Thus, MntABC was identified as a high-affinity Mn(2+) transporter in S. oligofermentans. mntA mutation reduced the survival of H2O2-pulsed S. oligofermentans 5.7-fold, while mntABC overexpression enhanced H2O2-challenged survival 12-fold, indicating that MntABC-mediated Mn(2+) uptake is pivotal to antioxidative stress in S. oligofermentans. perR mutation or H2O2 pulsing upregulated mntABC, while H2O2-induced upregulation diminished in the perR mutant. This suggests that perR represses mntABC expression but H2O2 can release the suppression. In conclusion, this work demonstrates that PerR regulates manganese homeostasis in S. oligofermentans, which is critical to H2O2 stress defenses and may be distributed across all oral streptococci lacking catalase. PMID:24487543

  12. Geology, Geochemistry and Re-Os systematics of manganese deposits from the Santa Rosalía Basin and adjacent areas in Baja California Sur, México

    NASA Astrophysics Data System (ADS)

    Del Rio Salas, R.; Ruiz, J.; Ochoa-Landín, L.; Noriega, O.; Barra, F.; Meza-Figueroa, D.; Paz-Moreno, F.

    2008-06-01

    The manganese ores in the Santa Rosalía region, western Mexico, are mainly stratiform horizons or mantos, constrained to the initial stages of sedimentary cycles of the Miocene Boléo Formation. The manganese mineralization is generally restricted to isolated paleo-basins and related to NW-SE faults formed during the early stages of the opening of the Gulf of California. Jasper, Fe, and Mn oxides associated to the NW-SE structures may represent feeder zones for the mineralized system. The manganese oxide minerals include pyrolusite, cryptomelane, todorokite, hollandite, jacobsite, and pyrochroite. Trace elements in the manganese ores indicate a hydrothermal origin for the deposits of the Santa Rosalía area. Rare earth elements (REE) patterns obtained for manganese minerals from the Lucifer and El Gavilán deposits also support a hydrothermal origin, whereas the middle REE enrichment observed in samples from the Boléo district indicates mixing between hydrothermal and hydrogenous sources. Osmium and rhenium concentrations of the manganese minerals range between 33-173 ppt and 0.14-89 ppb, respectively. The initial 187Os/188Os ratios in the manganese oxides from Lucifer and the Boléo district range between 0.43 to 0.51 and 0.70 to 0.74, respectively. These ratios are different from seawater at 7 Ma (0.84-0.89), which suggests important contributions of osmium from underlying rocks such as the Miocene volcanic rocks and the Cretaceous quartz-monzonite basement. Field evidence, manganese oxide mineralogy coupled with major and trace element geochemistry and Re-Os systematics support a hydrothermal origin for the manganese deposits from the Santa Rosalía region. The ore deposition style indicates an exhalative-intraformational environment restricted to isolated basins in a diagenetic stage related to the initial evolution of the Gulf of California.

  13. The Cytochrome c Maturation Operon Is Involved in Manganese Oxidation in Pseudomonas putida GB-1

    PubMed Central

    de Vrind, J. P. M.; Brouwers, G. J.; Corstjens, P. L. A. M.; den Dulk, J.; de Vrind-de Jong, E. W.

    1998-01-01

    A Pseudomonas putida strain, strain GB-1, oxidizes Mn2+ to Mn oxide in the early stationary growth phase. It also secretes a siderophore (identified as pyoverdine) when it is subjected to iron limitation. After transposon (Tn5) mutagenesis several classes of mutants with differences in Mn2+ oxidation and/or secretion of the Mn2+-oxidizing activity were identified. Preliminary analysis of the Tn5 insertion site in one of the nonoxidizing mutants suggested that a multicopper oxidase-related enzyme is involved in Mn2+ oxidation. The insertion site in another mutant was preliminarily identified as a gene involved in the general protein secretion pathway. Two mutants defective in Mn2+-oxidizing activity also secreted porphyrins into the medium and appeared to be derepressed for pyoverdine production. These strains were chosen for detailed analysis. Both mutants were shown to contain Tn5 insertions in the ccmF gene, which is part of the cytochrome c maturation operon. They were cytochrome oxidase negative and did not contain c-type cytochromes. Complementation with part of the ccm operon isolated from the wild type restored the phenotype of the parent strain. These results indicate that a functional ccm operon is required for Mn2+ oxidation in P. putida GB-1. A possible relationship between porphyrin secretion resulting from the ccm mutation and stimulation of pyoverdine production is discussed. PMID:9758767

  14. Effects of NOM on Oxidative Reactivity of Manganese Dioxide in Binary Oxide Mixtures with Goethite or Hematite.

    PubMed

    Zhang, Huichun; Taujale, Saru; Huang, Jianzhi; Lee, Gang-Juan

    2015-03-10

    MnO2 typically coexists with iron oxides as either discrete particles or coatings in soils and sediments. This work examines the effect of Aldrich humic acid (AHA), alginate, and pyromellitic acid (PA) as representative natural organic matter (NOM) analogues on the oxidative reactivity of MnO2, as quantified by pseudo-first-order rate constants of triclosan oxidation, in mixtures with goethite or hematite. Adsorption studies showed that there was low adsorption of the NOMs by MnO2, but high (AHA and alginate) to low (PA) adsorption by the iron oxides. Based on the ATR-FTIR spectra obtained for the adsorbed PA on goethite or goethite + MnO2, the adsorption of PA occurred mainly through formation of outer-sphere complexes. The Fe oxides by themselves inhibited MnO2 reactivity through intensive heteroaggregation between the positively charged Fe oxides and the negatively charged MnO2; the low solubility of the iron oxides limited surface complexation of soluble Fe(3+) with MnO2. In ternary mixtures of MnO2, Fe oxides, and NOM analogues, the reactivity of MnO2 varied from inhibited to promoted as compared with that in the respective MnO2 + NOM binary mixtures. The dominant interaction mechanisms include an enhanced extent of homoaggregation within the Fe oxides due to formation of oppositely charged patches within the Fe oxides but an inhibited extent of heteroaggregation between the Fe oxide and MnO2 at [AHA] < 2-4 mg-C/L or [alginate/PA] < 5-10 mg/L, and an inhibited extent of heteroaggregation due to the largely negatively charged surfaces for all oxides at [AHA] > 4 mg-C/L or [alginate/PA] > 10 mg/L. PMID:25652230

  15. Oxidation state of manganese in zinc pyrophosphate: Probed by luminescence and EPR studies

    SciTech Connect

    Gupta, Santosh K., E-mail: santoshg@barc.gov.in; Kadam, R. M., E-mail: santoshg@barc.gov.in; Natarajan, V., E-mail: santoshg@barc.gov.in; Godbole, S. V., E-mail: santoshg@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

    2014-04-24

    Zn{sub 2}P{sub 2}O{sub 7}: Mn was synthesized by wet chemical route and characterized by X-ray diffraction (XRD), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. Photoluminescence spectrum shows two bands, one at 500 nm (green emission), which is attributed to the {sup 4}T{sub 1}({sup 4}G)-{sup 6}A{sub 1}({sup 6}S) transition of Mn{sup 2+} and other centered at 686 nm (red emission) is attributed to the electronic transition between {sup 2}E and {sup 4}A{sub 2} of Mn{sup 4+} accompanied with vibronic transitions. EPR spectroscopic studies also confirmed the presence of both Mn2+ and Mn4+ ions in zinc pyrophosphate with difference in the number of fine transitions and g values (Mn{sub 4+}, S=3/2, three fine transitions and g < 2.00; Mn{sup 2+} S=5/2, five fine transitions and g=2.00).Mn{sup 2+} is attributed to presence of Mn at 6-ccordinated Zn{sup 2+} site whereas Mn{sup 4+} is due to presence substitution of Mn{sup 4+} at Zn{sup 2+} site thereby invoking charge compensation by presence of interstitial oxygen ions around Mn{sup 4+} ion or due to substitution of manganese at distorted 5-coordinated zinc site.

  16. Oxidation state of manganese in zinc pyrophosphate: Probed by luminescence and EPR studies

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Kadam, R. M.; Natarajan, V.; Godbole, S. V.

    2014-04-01

    Zn2P2O7: Mn was synthesized by wet chemical route and characterized by X-ray diffraction (XRD), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. Photoluminescence spectrum shows two bands, one at 500 nm (green emission), which is attributed to the 4T1(4G)-6A1(6S) transition of Mn2+ and other centered at 686 nm (red emission) is attributed to the electronic transition between 2E and 4A2 of Mn4+ accompanied with vibronic transitions. EPR spectroscopic studies also confirmed the presence of both Mn2+ and Mn4+ ions in zinc pyrophosphate with difference in the number of fine transitions and g values (Mn4+, S=3/2, three fine transitions and g < 2.00; Mn2+ S=5/2, five fine transitions and g=2.00).Mn2+ is attributed to presence of Mn at 6-ccordinated Zn2+ site whereas Mn4+ is due to presence substitution of Mn4+ at Zn2+ site thereby invoking charge compensation by presence of interstitial oxygen ions around Mn4+ ion or due to substitution of manganese at distorted 5-coordinated zinc site.

  17. Mesoporous manganese oxide nanowires for high-capacity, high-rate, hybrid electrical energy storage.

    PubMed

    Yan, Wenbo; Ayvazian, Talin; Kim, Jungyun; Liu, Yu; Donavan, Keith C; Xing, Wendong; Yang, Yongan; Hemminger, John C; Penner, Reginald M

    2011-10-25

    Arrays of mesoporous manganese dioxide, mp-MnO(2), nanowires were electrodeposited on glass and silicon surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. The electrodeposition procedure involved the application, in a Mn(ClO(4))(2)-containing aqueous electrolyte, of a sequence of 0.60 V (vs MSE) voltage pulses delineated by 25 s rest intervals. This "multipulse" deposition program produced mp-MnO(2) nanowires with a total porosity of 43-56%. Transmission electron microscopy revealed the presence within these nanowires of a network of 3-5 nm diameter fibrils that were X-ray and electron amorphous, consistent with the measured porosity values. mp-MnO(2) nanowires were rectangular in cross-section with adjustable height, ranging from 21 to 63 nm, and adjustable width ranging from 200 to 600 nm. Arrays of 20 nm × 400 nm mp-MnO(2) nanowires were characterized by a specific capacitance, C(sp), of 923 ± 24 F/g at 5 mV/s and 484 ± 15 F/g at 100 mV/s. These C(sp) values reflected true hybrid electrical energy storage with significant contributions from double-layer capacitance and noninsertion pseudocapacitance (38% for 20 nm × 400 nm nanowires at 5 mV/s) coupled with a Faradaic insertion capacity (62%). These two contributions to the total C(sp) were deconvoluted as a function of the potential scan rate. PMID:21942449

  18. Biodiesel synthesis catalyzed by transition metal oxides: ferric-manganese doped tungstated/molybdena nanoparticle catalyst.

    PubMed

    Alhassan, Fatah Hamid; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The solid acid Ferric-manganese doped tungstated/molybdena nananoparticle catalyst was prepared via impregnation reaction followed by calcination at 600°C for 3 h. The characterization was done using X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), X-ray fluorescence (XRF), Transmission electron microscope (TEM) and Brunner-Emmett-Teller surface area measurement (BET). Moreover, dependence of biodiesel yield on the reaction variables such as the reaction temperature, catalyst loading, as well as molar ratio of methanol/oil and reusability were also appraised. The catalyst was reused six times without any loss in activity with maximum yield of 92.3% ±1.12 achieved in the optimized conditions of reaction temperature of 200°C; stirring speed of 600 rpm, 1:25 molar ratio of oil to alcohol, 6 % w/w catalyst loading as well as 8 h as time of the reaction. The fuel properties of WCOME's were evaluated, including the density, kinematic viscosity, pour point, cloud point and flash point whereas all properties were compared with the limits in the ASTM D6751 standard. PMID:25492234

  19. An anionic N-donor ligand promotes manganese-catalyzed water oxidation

    PubMed Central

    Young, Karin J.; Takase, Michael K.; Brudvig, Gary W.

    2014-01-01

    Four manganese complexes of pentadentate ligands have been studied for their ability to act as oxygen-evolution catalysts in the presence of Oxone or hydrogen peroxide. The complexes [Mn(PaPy3)(NO3)](ClO4), 1 (PaPy3H = N,N-bis(2-pyridylmethyl)-amine-N-ethyl-2-pyridine-2-carboxamide) and [Mn(PaPy3)(?-O)(PaPy3)Mn](ClO4)2, 2 feature an anionic carboxamido ligand trans to the labile sixth coordination site, while [Mn(N4Py)OTf](OTf), 3 (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [Mn(PY5)(OH2)](ClO4)2, 4 (PY5 = 2,6-bis(bis(2-pyridyl)methoxymethane)-pyridine) have neutral ligands of varying flexibility. 1 and 2 are shown to evolve oxygen in the presence of either Oxone or hydrogen peroxide, but 3 evolves oxygen only in the presence of hydrogen peroxide and 4 is inactive. The activity of 1 and 2 with Oxone suggests that the presence of an anionic N-donor ligand plays a role in stabilizing putative high-valent intermediates. Anionic N-donor ligands may be viewed as an alternative to ?-oxo ligands that are prone to protonation in low-valent Mn species formed during a catalytic cycle, resulting in loss of catalyst structure. PMID:23777320

  20. Thermal chemistry of Mn{sub 2}(CO){sub 10} during deposition of thin manganese films on silicon oxide and on copper surfaces

    SciTech Connect

    Qin Xiangdong; Sun Huaxing; Zaera, Francisco [Department of Chemistry, University of California, Riverside, California 92521 (United States)

    2012-01-15

    The surface chemistry of dimanganese decacarbonyl on the native oxide of Si(100) wafers was characterized with the aid of x-ray photoelectron spectroscopy. Initial experiments in a small stainless-steel reactor identified a narrow range of temperatures, between approximately 445 and 465 K, in which the deposition of manganese could be achieved in a self-limiting fashion, as is desirable for atomic layer deposition. Deposition at higher temperatures leads to multilayer growth, but the extent of this Mn deposition reverses at even higher temperatures (about 625 K), and also ifhydrogen is added to the reaction mixture. Extensive decarbonylation takes place below room temperature, but limited C-O bond dissociation and carbon deposition are still seen after high exposures at 625 K. The films deposited at low ({approx}450 K) temperatures are mostly in the form of MnO, but at 625 K that converts to a manganese silicate, and upon higher doses a manganese silicide forms at the SiO{sub 2}/Si(100) interface as well. No metallic manganese could be deposited with this precursor on either silicon dioxide or copper surfaces.

  1. Manganese oxidation in pH and O2 microenvironments produced by phytoplankton

    NASA Technical Reports Server (NTRS)

    Richardson, Laurie L.; Aguilar, Carmen; Nealson, Kenneth H.

    1988-01-01

    This paper reports on the oxidation of Mn(II) by pure cultures of Chlorella. It is shown that these cultures establish strong microgradients of pH and O2 concentration due to their photosynthetic activity, and it is demonstrated that Mn oxidation in the pelagic zone of Oneida Lake, New York, is limited to a microzone of high pH and O2 associated with the near-surface aggregates of phytoplankton cells. The data suggest that visible light is important in catalyzing Mn oxidation by driving the photosynthetic removal of CO2 with concomitant increases in pH.

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

    Microsoft Academic Search

    Chris A. Francis; Bradley M. Tebo

    2002-01-01

    Bacterial spores are renowned for their longevity, ubiquity, and resistance to environmental insults, but virtually nothing is known regarding whether these metabolically dormant structures impact their surrounding chemical environments. In the present study, a number of spore-forming bacteria that produce dormant spores which enzymatically oxidize soluble Mn(II) to insoluble Mn(IV) oxides were isolated from coastal marine sediments. The highly charged

  3. Distribution and speciation of trace elements in iron and manganese oxide cave deposits

    SciTech Connect

    Frierdich, Andrew J.; Catalano, Jeffrey G. (WU)

    2012-10-24

    Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redox conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.

  4. Protective effects of antioxidants and anti-inflammatory agents against manganese-induced oxidative damage and neuronal injury

    SciTech Connect

    Milatovic, Dejan, E-mail: dejan.milatovic@vanderbilt.edu [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States)] [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States); Gupta, Ramesh C. [Murray State University, Breathitt Veterinary Center, Hopkinsville, KY (United States)] [Murray State University, Breathitt Veterinary Center, Hopkinsville, KY (United States); Yu, Yingchun; Zaja-Milatovic, Snjezana [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States)] [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States); Aschner, Michael [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States) [Vanderbilt University School of Medicine, Department of Pediatrics, Nashville, TN (United States); Pharmacology and the Kennedy Center for Research on Human Development, Nashville, TN (United States)

    2011-11-15

    Exposure to excessive manganese (Mn) levels leads to neurotoxicity, referred to as manganism, which resembles Parkinson's disease (PD). Manganism is caused by neuronal injury in both cortical and subcortical regions, particularly in the basal ganglia. The basis for the selective neurotoxicity of Mn is not yet fully understood. However, several studies suggest that oxidative damage and inflammatory processes play prominent roles in the degeneration of dopamine-containing neurons. In the present study, we assessed the effects of Mn on reactive oxygen species (ROS) formation, changes in high-energy phosphates and associated neuronal dysfunctions both in vitro and in vivo. Results from our in vitro study showed a significant (p < 0.01) increase in biomarkers of oxidative damage, F{sub 2}-isoprostanes (F{sub 2}-IsoPs), as well as the depletion of ATP in primary rat cortical neurons following exposure to Mn (500 {mu}M) for 2 h. These effects were protected when neurons were pretreated for 30 min with 100 of an antioxidant, the hydrophilic vitamin E analog, trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), or an anti-inflammatory agent, indomethacin. Results from our in vivo study confirmed a significant increase in F{sub 2}-IsoPs levels in conjunction with the progressive spine degeneration and dendritic damage of the striatal medium spiny neurons (MSNs) of mice exposed to Mn (100 mg/kg, s.c.) 24 h. Additionally, pretreatment with vitamin E (100 mg/kg, i.p.) or ibuprofen (140 {mu}g/ml in the drinking water for two weeks) attenuated the Mn-induced increase in cerebral F{sub 2}-IsoPs? and protected the MSNs from dendritic atrophy and dendritic spine loss. Our findings suggest that the mediation of oxidative stress/mitochondrial dysfunction and the control of alterations in biomarkers of oxidative injury, neuroinflammation and synaptodendritic degeneration may provide an effective, multi-pronged therapeutic strategy for protecting dysfunctional dopaminergic transmission and slowing of the progression of Mn-induced neurodegenerative processes. -- Research highlights: Black-Right-Pointing-Pointer Mn exposure leads to neurotoxicity in vitro and in vivo. Black-Right-Pointing-Pointer Antioxidants and anti-inflammatory agents attenuate Mn-induced oxidative injury. Black-Right-Pointing-Pointer These agents also protect the striatal neurons from dendritic atrophy and spine loss. Black-Right-Pointing-Pointer These prophylactic strategies may be effective against Mn neurotoxicity.

  5. Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

    1989-01-01

    The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

  6. In Situ XAS and XRD Studies of Substituted Spinel Lithium Manganese Oxides in the 4-5 V Region

    SciTech Connect

    McBreen, J.; Mukerjee, S.; Yang, X. Q.; Sun, X.; Ein-Eli, Y.

    1998-11-01

    Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the phase behavior of the cathode. Substitution with either metal or with a combination of both shortens the 4.2 V plateau and results in higher voltage plateaus. In situ x-ray absorption (XAS) studies indicate that the higher voltage plateaus are related to redox processes on the substituents. In situ x-ray diffraction (XRD) on LiCu{sub 0.5}Mn{sub 1.5}O{sub 4} shows single phase behavior during the charge and discharge process. Three phases are observed for LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} and two phases are observed in the case of LiNi{sub 0.25}Cu{sub 0.25}Mn{sub 1.5}O{sub 4}. The electrolyte stability is dependent on both the operating voltage and the cathode composition. Even though Ni substituted materials have lower voltages, the electrolyte is more stable in cells with the Cu substituted materials.

  7. One-pot synthesis of manganese oxide-carbon composite microspheres with three dimensional channels for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ko, You Na; Park, Seung Bin; Choi, Seung Ho; Kang, Yun Chan

    2014-08-01

    The fabrication of manganese oxide-carbon composite microspheres with open nanochannels and their electrochemical performance as anode materials for lithium ion batteries are investigated. Amorphous-like Mn3O4 nanoparticles embedded in a carbon matrix with three-dimensional channels are fabricated by one-pot spray pyrolysis. The electrochemical properties of the Mn3O4 nanopowders are also compared with those of the Mn3O4-C composite microspheres possessing macropores resembling ant-cave networks. The discharge capacity of the Mn3O4-C composite microspheres at a current density of 500 mA g-1 is 622 mA h g-1 after 700 cycles. However, the discharge capacity of the Mn3O4 nanopowders is as low as 219 mA h g-1 after 100 cycles. The Mn3O4-C composite microspheres with structural advantages and high electrical conductivity have higher initial discharge and charge capacities and better cycling and rate performances compared to those of the Mn3O4 nanopowders.

  8. Electrochemical and structural characterization of titanium-substituted manganese oxides based on Na0.44MnO2

    SciTech Connect

    Doeff, Marca M.; Richardson, Thomas J.; Hwang, Kwang-Taek

    2004-03-01

    A series of titanium-substituted manganese oxides, Li{sub x}Ti{sub y}Mn{sub 1-y}O{sub 2} (y = 0.11, 0.22, 0.33, 0.44, and 0.55) with the Na{sub 0.44}MnO{sub 2} structure were prepared from Na{sub x}Ti{sub y}Mn{sub 1-y}O{sub 2} (x {approx} 0.44) precursors. The electrochemical characteristics of these compounds, which retain the unique double-tunnel structure during ion exchange, were examined in lithium/polymer electrolyte cells operating at 85 C. All of the substituted cathode materials intercalated lithium reversibly, with Li{sub x}Ti{sub 0.22}Mn{sub 0.78}O{sub 2} exhibiting the highest capacity in polymer cells, about 10-20% greater than that of unsubstituted Li{sub x}MnO{sub 2} made from Na{sub 0.44}MnO{sub 2}. In common with Li{sub x}MnO{sub 2}, the Ti-substituted materials exhibited good capacity retention over one hundred or more cycles, with some compositions exhibiting a fade rate of less than 0.03% per cycle.

  9. Catalytic degradation of Acid Orange 7 by manganese oxide octahedral molecular sieves with peroxymonosulfate under visible light irradiation.

    PubMed

    Duan, Lian; Sun, Binzhe; Wei, Mingyu; Luo, Shilu; Pan, Fei; Xu, Aihua; Li, Xiaoxia

    2015-03-21

    In this paper, the photodegradation of Acid Orange 7 (AO7) in aqueous solutions with peroxymonosulfate (PMS) was studied with manganese oxide octahedral molecular sieves (OMS-2) as the catalyst. The activities of different systems including OMS-2 under visible light irradiation (OMS-2/Vis), OMS-2/PMS and OMS-2/PMS/Vis were evaluated. It was found that the efficiency of OMS-2/PMS was much higher than that of OMS-2/Vis and could be further enhanced by visible light irradiation. The catalyst also exhibited stable performance for multiple runs. Results from ESR and XPS analyses suggested that the highly catalytic activity of the OMS-2/PMS/Vis system possible involved the activation of PMS to sulfate radicals meditated by the redox pair of Mn(IV)/Mn(III) and Mn(III)/Mn(II), while in the OMS-2/PMS system, only the redox reaction between Mn(IV)/Mn(III) occurred. Several operational parameters, such as dye concentration, catalyst load, PMS concentration and solution pH, affected the degradation of AO7. PMID:25528234

  10. The expression of manganese superoxide dismutase gene from Nelumbo nucifera responds strongly to chilling and oxidative stresses.

    PubMed

    Li, Wen; Qi, Lin; Lin, Xiaodong; Chen, Huhui; Ma, Zhanqi; Wu, Keqiang; Huang, Shangzhi

    2009-03-01

    A manganese superoxide dismutase (Mn-SOD) gene, NnMSD1, was identified from embryonic axes of the sacred lotus (Nelumbo nucifera Gaertn.). The NnMSD1 protein contains all conserved residues of the Mn-SOD protein family, including four consensus metal binding domains and a signal peptide for mitochondrial targeting. Southern blot analysis suggests the existence of two Mn-SOD genes in sacred lotus. NnMSD1 was highly expressed in developing embryonic axes during seed development, but appeared in cotyledons only at the early stage of development and became undetectable in the cotyledons during late embryogenesis. The expression of the NnMSD1 gene in germinating embryonic axes, in response to various stresses such as heat shock, chilling, and exposure to stress-related chemicals, was also studied. Heat shock strongly inhibited the expression of the NnMSD1 gene, whereas the NnMSD1 transcript level increased strongly in chilling stress treatment. An increase in expression was also highly induced by H2O2 in germinating embryonic axes. The results suggest that the expression pattern of the NnMSD1 gene differed between developing axes and cotyledons, and that the NnMSD1 gene expression responds strongly to chilling and oxidative stress. PMID:19261071

  11. One-pot synthesis of co-substituted manganese oxide nanosheets and physical properties of lamellar aggregates

    SciTech Connect

    Kai, Kazuya [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan) [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan); Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Cuisinier, Marine [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan) [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan); Institut des Materiaux Jean Rouxel (IMN), CNRS UMR 6502, Universite de Nantes, 2 Rue de la Houssiniere, BP32229, 44322 Nantes Cedex 3 (France); Yoshida, Yukihiro; Saito, Gunzi [Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) [Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Research Institute, Meijo University, Shiogamaguchi 1-501 Tempaku-ku, Nagoya 468-8502 (Japan); Kobayashi, Yoji [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)] [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan); Kageyama, Hiroshi, E-mail: kage@scl.kyoto-u.ac.jp [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan) [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan); Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)

    2012-11-15

    Graphical abstract: Display Omitted Highlights: ? Solid solution nanosheets, (Mn{sub 1?x}Co{sub x})O{sub 2}, synthesized via facile one-pot process. ? The structural characterization of nanosheets revealing a single (Mn,Co)O{sub 2} layer and the solubility limit as x ? 0.20. ? The invariant charge density of the layer upon Co substitution. ? Systematic dependence of magnetic and optical properties of the lamellar aggregates. -- Abstract: Co-substituted manganese oxide nanosheets, (Mn{sub 1?x}Co{sub x})O{sub 2} have been synthesized in the form of a colloidal suspension via a simple one-pot method. Substitution effects on the structural, optical absorption, and magnetic properties are investigated for the nanosheets and their lamellar aggregates. The composition of the (Mn{sub 1?x}Co{sub x})O{sub 2} nanosheets can be controlled continuously by adjusting the molar ratio of the starting materials. The solubility limit is x ? 0.20 based on the cell volume. In the 0.00 ? x ? 0.20 range, the band gap energy, magnetic moment, and Weiss temperature change systematically with x. The charge density of the (Mn,Co)O{sub 2} layer is independent of x (i.e., [(Mn,Co)O{sub 2}]{sup 0.2?}) and the cobalt ions are trivalent in low-spin state.

  12. YREE sorption on hydrous manganese oxide (MnOx) in 0.5 M NaCl

    NASA Astrophysics Data System (ADS)

    Marshall, K. S.; Schijf, J.

    2010-12-01

    Cerium is the only member of the yttrium and rare earth element (YREE) series that can be oxidized in natural waters from Ce(III) to less soluble Ce(IV), causing anomalous sorption behavior with respect to its strictly trivalent YREE neighbors. Sedimentary Ce anomaly records have been interpreted in terms of episodic shifts in the bottom water oxygenation of the paleo-ocean. However, Ce anomalies also form due to catalytic Ce oxidation on certain sorbent surfaces regardless of ambient redox conditions, thus creating a ‘preformed’ signal that may instead reflect variations in the composition of settling particles. We investigate YREE sorption in 0.5 M NaCl on mixtures of three major components of marine particulate matter: Fe and Mn oxides, and algal debris. Here we report our results for one pure endmember, hydrous manganese oxide (MnOx). Batch experiments with freshly prepared MnOx were conducted under nitrogen atmosphere, to prevent aerobic Ce oxidation and YREE complexation with carbonate, over a range of pH (4-8) at 25.0±0.1°C. After at least 6 hours of equilibration at each pH, solution samples were filtered to 0.22 ?m and dissolved YREE concentrations analyzed by ICP-MS to determine their solid/solution distribution coefficient, K. Under the same experimental conditions, log K increases less steeply with pH for MnOx than for hydrous ferric oxide (HFO). This may result from the lower pHzpc of MnOx as well as its higher tendency than HFO to form bidentate edge-sharing YREE surface complexes, as determined by others using X-ray Absorption Fine Structure (XAFS) spectroscopy. A non-electrostatic surface complexation model is being developed to further elucidate these findings. Preferential Ce sorption, implying catalytic Ce oxidation at the mineral-water interface, was observed on MnOx but never on HFO or organic surfaces, in agreement with prior research. This may be related to the generally higher Gibbs free energy gain associated with oxidation reactions in which MnOx is the electron acceptor, although some large organic ligands, such as siderophores, have also been reported to catalyze Ce(III) oxidation. The enhanced Ce removal in anoxic 0.5 M NaCl solutions increases with pH from about 10- to 100-fold relative to the other YREEs, which show comparatively little fractionation among themselves. Sedimentary Ce anomalies are therefore unlikely to provide a reliable and lasting record of bottom water oxygenation when Mn oxides are an important constituent of settling particles and their interpretation as a proxy of paleo-redox conditions should be undertaken with appropriate caution.

  13. Manganese Intoxication

    PubMed Central

    Hine, Charles H.; Pasi, Aurelio

    1975-01-01

    We have reported two cases of chronic manganese poisoning. Case 1 followed exposure to manganese fumes in cutting and burning manganese steel. Case 2 resulted from exposure to dusts of manganese dioxide, an ingredient used in glazing of ceramics. There were initial difficulties in establishing the correct diagnosis. Prominent clinical features were severe and persistent chronic depressive psychosis (Case 1), transient acute brain syndrome (Case 2) and the presence of various extrapyramidal symptoms in both cases. Manganese intoxication has not previously been reported as occurring in California. With increasing use of the metal, the disease should be considered in the differential diagnosis of neurologic and psychiatric disease. Our observations were made in the period 1964 through 1968. Recently the prognosis of victims of manganese poisoning has been improved dramatically by the introduction of levodopa as a therapeutic agent. PMID:1179714

  14. Pseudocapacitive mechanism of manganese oxide in 1-ethyl-3-methylimidazolium thiocyanate ionic liquid electrolyte studied using X-ray photoelectron spectroscopy.

    PubMed

    Chang, Jeng-Kuei; Lee, Ming-Tsung; Tsai, Wen-Ta; Deng, Ming-Jay; Cheng, Hui-Fang; Sun, I-Wen

    2009-10-01

    The electrochemical behavior of anodically deposited manganese oxide was studied in pyrrolidinium formate (P-HCOO), 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6), and 1-ethyl-3-methylimidazolium thiocyanate (EMI-SCN) ionic liquids (ILs). The experimental data indicate that the Mn oxide electrode showed ideal pseudocapacitive performance in aprotic EMI-SCN IL. In a potential window of approximately 1.5 V, the oxide specific capacitance, evaluated using cyclic voltammetry and chronopotentiometry, was about 55 F/g. The electrochemical energy storage reaction was examined using X-ray photoelectron spectroscopy (XPS). It was confirmed that the SCN- anions, instead of the EMI+ cations, were the primary working species that can become incorporated into the oxide and thus compensate the Mn3+/Mn4+ valent state variation upon the charge-discharge process. According to the analytical results, a pseudocapacitive mechanism of Mn oxide in the SCN- based aprotic IL was proposed. PMID:19621902

  15. 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 ?M 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 ?g g(-1) d(-1) and in the absence, it was 0.17 ?g 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 Alcanivorax sp. PMID:24183631

  16. Relationship of manganese-iron oxides and associated heavy metals to grain size in stream sediments

    USGS Publications Warehouse

    Whitney, P.R.

    1975-01-01

    The distribution of ammonium citrate-leachable lead, zinc and cadmium among size fractions in stream sediments is strongly influenced by the presence of hydrous Mn-Fe oxides in the form of coatings on sediment grains. Distribution curves showing leachable metals as a function of particle size are given for eight samples from streams in New York State. These show certain features in common; in particular two concentrations of metals, one in the finest fractions, and a second peak in the coarse sand and gravel fraction. The latter can be explained as a result of the increasing prevalence and thickness of oxide coatings with increasing particle size, with the oxides serving as collectors for the heavy metals. The distribution of Zn and Cd in most of the samples closely parallels that of Mn; the distribution of Pb is less regular and appears to be related to Fe in some samples and Mn in others. The concentration of metals in the coarse fractions due to oxide coatings, combined with the common occurrence of oxide deposition in streams of glaciated regions, raises the possibility of using coarse materials for geochemical surveys and environmental heavy-metal studies. ?? 1975.

  17. Electrochemical performance evaluation of polyaniline\\/lithium manganese nickel oxide composites synthesized using surfactant agents

    Microsoft Academic Search

    Silmara Neves; Sheila C. Canobre; Rafael S. Oliveira; Carla Polo Fonseca

    2009-01-01

    The effect of adding a non-ionic surfactant to disperse oxide particles on the electrochemical performance of PAni\\/LiMnNiO4 composites is evaluated by using cyclic voltammetry (CV), impedance measurements and constant-current charge\\/discharge cycling techniques. Three surfactants based on ethoxylated (EO) and propoxylated (PO) lauryl alcohols (3EO\\/6PO, L306; 4EO\\/5PO, L405; and 6EO\\/3PO, L603) were investigated. For comparative purposes, the oxide and polyaniline were

  18. Kinetics of chromium(II) oxidation to chromium(VI) by reaction with manganese dioxide

    Microsoft Academic Search

    L. Edmond Eary; Dhanpat Rai

    1987-01-01

    The kinetics of oxidation of aqueous Cr(III) to Cr(VI) by reaction with pyrolusite (..beta..-MnOâ(s)) were studied in aerated and deaerated solutions at 27°C for pH 3.0-10.1, for 10\\/sup -4.7\\/-10\\/sup -3.4\\/ M Cr(III), and as a function of ..beta..-MnOâ(s) surface area to assess the possible effects on Cr transport in industrial waste materials. The oxidation of aqueous Cr(III) is not appreciably

  19. Manganese-oxidizing and -reducing microorganisms isolated from biofilms in chlorinated drinking water systems

    E-print Network

    Falkinham, Joseph

    -oxidizing and -reducing bacteria in conventional water treatment plants exposed to different levels of chlorine. Mn (II Organization, 1998). Mn accumulation and release can be a costly and diffi- cult problem for drinking water water systems Jose´ M. Cerrato a , Joseph O. Falkinham, IIIb , Andrea M. Dietrich a, *, William R

  20. MOLECULAR-LEVEL PROCESS GOVERNING THE INTERACTION OF CONTAMINANTS WITH IRON AND MANGANESE OXIDES

    EPA Science Inventory

    Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on stru...

  1. The inhibitory effect of manganese on acetylcholinesterase activity enhances oxidative stress and neuroinflammation in the rat brain

    PubMed Central

    Santos, Dinamene; Milatovic, Dejan; Andrade, Vanda; Camila, Batoreu M.; Aschner, Michael; Marreilha dos Santos, A.P.

    2011-01-01

    Background Manganese (Mn) is a naturally occurring element and an essential nutrient for humans and animals. However, exposure to high levels of Mn may cause neurotoxic effects. The pathological mechanisms associated with Mn neurotoxicity are poorly understood, but several reports have established it is mediated, at least in part, by oxidative stress. Objectives The present study was undertaken to test the hypothesis that a decrease in acetylcholinesterase (AChE) activity mediates Mn-induced neurotoxicity. Methods Groups of 6 rats received 4 or 8 intraperitoneal (i.p.) injections of 25 mg MnCl2/kg/day, every 48 hours. Twenty-four hours after the last injection, brain AChE activity and the levels of F2-isoprostanes (F2-IsoPs) and F4-neuroprostanes (F4-NPs) (biomarkers of oxidative stress), as well as prostaglandin E2 (PGE2) (biomarker of neuroinflammation) were analyzed. Results The results showed that after either 4 or 8 Mn doses, brain AChE activity was significantly decreased (p<0.05), to 60 ± 16 % and 55 ± 13 % of control levels, respectively. Both treated groups exhibited clear signs of neurobehavioral toxicity, characterized by a significant (p<0.001) decrease in ambulation and rearings in open-field. Furthermore, Mn treatment caused a significant increase (p<0.05) in brain F2-IsoPs and PGE2 levels, but only after 8 doses. In rats treated with 4 Mn doses, a significant increase (p<0.05) in brain F4-NPs levels was found. To evaluate cellular responses to oxidative stress, we assessed brain nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) and Mn-superoxide dismutase (Mn-SOD, SOD2) protein expression levels. A significant increase in Mn-SOD protein expression (p<0.05) and a trend towards increased Nrf2 protein expression was noted in rat brains after 4 Mn doses vs. the control group, but the expression of these proteins was decreased after 8 Mn doses. Taken together, these results suggest that the inhibitory effect of Mn on AChE activity promotes increased neuronal oxidative stress and neuroinflammatory biomarkers. PMID:22154916

  2. Evaluation of the chronic inhalation toxicity of a manganese oxide aerosol--I. Introduction, experimental design, and aerosol generation methods.

    PubMed

    Ulrich, C E; Rinehart, W; Busey, W

    1979-03-01

    A brief literature review on manganese toxicity is presented; as related to designing a chronic inhalation study for evaluating methylcyclopentadienyl manganese tricarbonyl when utilized as a motor fuel additive. The experimental design of this study is described. The generation system utilized to simulate the manganese aerosol produced by an internal combustion engine is described in detail. This generation system operated twenty-four hours per day, seven days per week producing aerosols at 11.6, 112.5, and 1152 micrograms Mn/m3 with an aerodynamic diameter of approximately 0.11 micron. PMID:91319

  3. Manganese valence in oxides formed from in situ chemical oxidation of TCE by KMnO4.

    PubMed

    Loomer, Diana B; Al, Tom A; Banks, Vernon J; Parker, Beth L; Mayer, K Ulrich

    2010-08-01

    Batch and column experiments designed to simulate in situ chemical oxidation (ISCO) in a sand aquifer were conducted to create Mn-oxides (MnOx) by oxidation of trichloroethylene (TCE) with permanganate (MnO4-). Electron energy-loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) were used to quantify Mn valence in the oxides. The valence of Mn in the MnOx generated in near-source ISCO conditions was 2.2 and 2.3 when formed at low (<3) and neutral (6-7) pH conditions, respectively. There is no significant difference between these values. Valence was found to be sensitive to the preparation method and to aging. When formed in the presence of excess MnO4-, or aged for 3 months, Mn valence ranged from 2.5 to 3.6. Aging in a lower pH environment inhibited Mn oxidation. The EELS and XPS methods provided similar results, but there was a slight bias to higher values for XPS. This work demonstrates that MnO2(s) may not be the main product of MnO4- reaction with chlorinated solvents as is commonly assumed and that the efficiency of ISCO treatment may be greater than previously known. PMID:20617842

  4. Mechanism, decomposition pathway and new evidence for self-healing of manganese oxides as efficient water oxidizing catalysts: new insights.

    PubMed

    Najafpour, Mohammad Mahdi; Kompany-Zareh, Mohsen; Zahraei, Ali; Jafarian Sedigh, Davood; Jaccard, Hugues; Khoshkam, Maryam; Britt, R David; Casey, William H

    2013-10-28

    The electrochemical water-oxidation reaction usually requires a catalyst to reduce the overpotential and Earth-abundant catalysts, like MnO2, are attracting much attention. Here we use chemometric analysis, EPR and UV-Vis spectroscopies to track Mn(II) and MnO4(-) byproducts to the reaction of a MnO2 film in the presence of cerium(IV) ammonium nitrate. Permanganate ion is involved in at least two key reactions: it may oxidize water to O2 or can combine with Mn(II) to remake MnO2 solid. We propose mechanisms for water oxidation and present a self-healing process for this reaction. PMID:23982587

  5. Photosystem II like water oxidation mechanism in a bioinspired tetranuclear manganese complex.

    PubMed

    Liao, Rong-Zhen; Kärkäs, Markus D; Lee, Bao-Lin; Åkermark, Björn; Siegbahn, Per E M

    2015-01-01

    The synthesis of Mn-based catalysts to mimic the structural and catalytic properties of the oxygen-evolving complex in photosystem II is a long-standing goal for researchers. An interesting result in this field came with the synthesis of a Mn complex that enables water oxidation driven by the mild single-electron oxidant [Ru(bpy)3](3+). On the basis of hybrid density functional calculations, we herein propose a water oxidation mechanism for this bioinspired Mn catalyst, where the crucial O-O bond formation proceeds from the formal Mn4(IV,IV,IV,V) state by direct coupling of a Mn(IV)-bound terminal oxyl radical and a di-Mn bridging oxo group, a mechanism quite similar to the presently leading suggestion for the natural system. Of importance here is that the designed ligand is shown to be redox-active and can therefore store redox equivalents during the catalytic transitions, thereby alleviating the redox processes at the Mn centers. PMID:25486382

  6. A nano-sized manganese oxide in a protein matrix as a natural water-oxidizing site.

    PubMed

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

    2014-08-01

    The purpose of this review is to present recent advances in the structural and functional studies of water-oxidizing center of Photosystem II and its surrounding protein matrix in order to synthesize artificial catalysts for production of clean and efficient hydrogen fuel. PMID:24560883

  7. Manganese Complexes: Diverse Metabolic Routes to Oxidative Stress Resistance in Prokaryotes and Yeast

    PubMed Central

    2013-01-01

    Abstract Significance: Antioxidant enzymes are thought to provide critical protection to cells against reactive oxygen species (ROS). However, many organisms can fully compensate for the loss of such enzymatic defenses by accumulating metabolites and Mn2+, which can form catalytic Mn-antioxidants. Accumulated metabolites can direct reactivity of Mn2+ with superoxide and specifically shield proteins from oxidative damage. Recent Advances: There is mounting evidence that Mn-Pi (orthophosphate) complexes act as potent scavengers of superoxide in all three branches of life. Moreover, it is evident that Mn2+ in complexes with carbonates, peptides, nucleosides, and organic acids can also form catalytic Mn-antioxidants, pointing to diverse metabolic routes to oxidative stress resistance. Critical Issues: What conditions favor utility of Mn-metabolites versus enzymatic means for removing ROS? Mn2+-metabolite defenses are critical for preserving the activity of repair enzymes in Deinococcus radiodurans exposed to intense radiation stress, and in Lactobacillus plantarum, which lacks antioxidant enzymes. In other microorganisms, Mn-antioxidants can serve as an auxiliary protection when enzymatic antioxidants are insufficient or fail. These findings of a critical role of Mn-antioxidants in the survival of prokaryotes under oxidative stress parallel the trends developing for the simple eukaryote Saccharomyces cerevisiae. Future Directions: Phosphates, peptides and organic acids are just a snapshot of the types of anionic metabolites that promote such reactivity of Mn2+. Their probable roles in pathogen defense against the host immune response and in ROS-mediated signaling pathways are also areas that are worthy of serious investigation. Moreover, it is clear that these protective chemical processes can be harnessed for practical purposes. Antioxid. Redox Signal. 19, 933–944. PMID:23249283

  8. Topologically Constrained Manganese(III) and Iron(III) Complexes of Two Cross-Bridged Tetraazamacrocycles

    E-print Network

    Hubin, Tim

    Topologically Constrained Manganese(III) and Iron(III) Complexes of Two Cross prepared by the chemical oxidation of the divalent manganese and iron analogues. The ligands are ethylene for the complexes with manganese(III). The manganese chemistry of 1 was studied in depth. The dichloro manganese

  9. Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity.

    PubMed

    Arafa, Wael A A; Kärkäs, Markus D; Lee, Bao-Lin; Åkermark, Torbjörn; Liao, Rong-Zhen; Berends, Hans-Martin; Messinger, Johannes; Siegbahn, Per E M; Åkermark, Björn

    2014-06-28

    During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2(II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation. PMID:24554036

  10. Transformation of acetaminophen using manganese dioxide-mediated oxidative processes: reaction rates and pathways.

    PubMed

    Xiao, Hong; Song, Haiyan; Xie, Hongqin; Huang, Wei; Tan, Jun; Wu, Jianzhong

    2013-04-15

    This study investigates the oxidative transformation kinetics of acetaminophen (APAP) by ?-MnO2 under different conditions. APAP was rapidly oxidized by ?-MnO2 with the generation of Mn(2+). The measured APAP reaction rate considerably increased with an increase in initial ?-MnO2 and APAP concentration, but decreased as pH increased. The APAP reaction rate also increased with an increase in temperature. The addition of inorganic ions (Mn(2+), Ca(2+), and Fe(3+)) and substituted phenols (guaiacol, caffeic acid, and p-coumaric acid) as co-solutes remarkably decreased the transformation rate of APAP. The UV-Vis absorption spectra exhibited the ? ? ?* transition, typical for aromatic rings. In addition, the intensity of the absorption peak gradually improved with increasing reaction time, suggesting that APAP can polymerize to form oligomers. Moreover, the secondary mass spectra of the dimers elucidated that the dimers were formed by the covalent bonding of phenol aromatic rings. Moreover, the higher-degree oligomers were formed by the coupling polymerization of phenolic and anilidic groups of dimers. These results are useful in understanding the fate of APAP in natural systems. PMID:23434488

  11. Biodistribution and acute toxicity of a nanofluid containing manganese iron oxide nanoparticles produced by a mechanochemical process.

    PubMed

    Bellusci, Mariangela; La Barbera, Aurelio; Padella, Franco; Mancuso, Mariateresa; Pasquo, Alessandra; Grollino, Maria Giuseppa; Leter, Giorgio; Nardi, Elisa; Cremisini, Carlo; Giardullo, Paola; Pacchierotti, Francesca

    2014-01-01

    Superparamagnetic iron oxide nanoparticles are candidate contrast agents for magnetic resonance imaging and targeted drug delivery. Biodistribution and toxicity assessment are critical for the development of nanoparticle-based drugs, because of nanoparticle-enhanced biological reactivity. Here, we investigated the uptake, in vivo biodistribution, and in vitro and in vivo potential toxicity of manganese ferrite (MnFe2O4) nanoparticles, synthesized by an original high-yield, low-cost mechanochemical process. Cultures of murine Balb/3T3 fibroblasts were exposed for 24, 48, or 72 hours to increasing ferrofluid concentrations. Nanoparticle cellular uptake was assessed by flow-cytometry scatter-light measurements and microscopy imaging after Prussian blue staining; cytotoxicity was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and colony-forming assays. After a single intravenous injection, in vivo nanoparticle biodistribution and clearance were evaluated in mice by Mn spectrophotometric determination and Prussian blue staining in the liver, kidneys, spleen, and brain at different posttreatment times up to 21 days. The same organs were analyzed for any possible histopathological change. The in vitro study demonstrated dose-dependent nanoparticle uptake and statistically significant cytotoxic effects from a concentration of 50 ?g/mL for the MTT assay and 20 ?g/mL for the colony-forming assay. Significant increases in Mn concentrations were detected in all analyzed organs, peaking at 6 hours after injection and then gradually declining. Clearance appeared complete at 7 days in the kidneys, spleen, and brain, whereas in the liver Mn levels remained statistically higher than in vehicle-treated mice up to 3 weeks postinjection. No evidence of irreversible histopathological damage to any of the tested organs was observed. A comparison of the lowest in vitro toxic concentration with the intravenously injected dose and the administered dose of other ferrofluid drugs currently in clinical practice suggests that there might be sufficient safety margins for further development of our formulation. PMID:24790434

  12. Shewanella-mediated biosynthesis of manganese oxide micro-/nanocubes as efficient electrocatalysts for the oxygen reduction reaction.

    PubMed

    Jiang, Congcong; Guo, Zhaoyan; Zhu, Ying; Liu, Huan; Wan, Meixiang; Jiang, Lei

    2015-01-01

    Developing efficient electrocatalysts for the oxygen reduction reaction (ORR) is critical for promoting the widespread application of fuel cells and metal-air batteries. Here, we develop a biological low-cost, ecofriendly method for the synthesis of Mn2 O3 micro-/nanocubes by calcination of MnCO3 precursors in an oxygen atmosphere. Microcubic MnCO3 precursors with an edge length of 2.5??m were fabricated by dissimilatory metal-reducing Shewanella loihica PV-4 in the presence of MnO4 (-) as the sole electron acceptor under anaerobic conditions. After calcining the MnCO3 precursors at 500 and 700?°C, porous Mn2 O3 -500 and Mn2 O3 -700 also showed microcubic morphology, while their edge lengths decreased to 1.8??m due to thermal decomposition. Moreover, the surfaces of the Mn2 O3 microcubes were covered by granular nanoparticles with average diameters in the range of 18-202?nm, depending on the calcination temperatures. Electrochemical measurements demonstrated that the porous Mn2 O3 -500 micro-/nanocubes exhibit promising catalytic activity towards the ORR in an alkaline medium, which should be due to a synergistic effect of the overlapping molecular orbitals of oxygen/manganese and the hierarchically porous structures that are favorable for oxygen absorption. Moreover, these Mn2 O3 micro-/nanocubes possess better stability than commercial Pt/C catalysts and methanol-tolerance property in alkaline solution. Thus the Shewanella-mediated biosynthesis method we provided here might be a new strategy for the preparation of various transition metal oxides as high-performance ORR electrocatalysts at low cost. PMID:25425435

  13. Biodistribution and acute toxicity of a nanofluid containing manganese iron oxide nanoparticles produced by a mechanochemical process

    PubMed Central

    Bellusci, Mariangela; La Barbera, Aurelio; Padella, Franco; Mancuso, Mariateresa; Pasquo, Alessandra; Grollino, Maria Giuseppa; Leter, Giorgio; Nardi, Elisa; Cremisini, Carlo; Giardullo, Paola; Pacchierotti, Francesca

    2014-01-01

    Superparamagnetic iron oxide nanoparticles are candidate contrast agents for magnetic resonance imaging and targeted drug delivery. Biodistribution and toxicity assessment are critical for the development of nanoparticle-based drugs, because of nanoparticle-enhanced biological reactivity. Here, we investigated the uptake, in vivo biodistribution, and in vitro and in vivo potential toxicity of manganese ferrite (MnFe2O4) nanoparticles, synthesized by an original high-yield, low-cost mechanochemical process. Cultures of murine Balb/3T3 fibroblasts were exposed for 24, 48, or 72 hours to increasing ferrofluid concentrations. Nanoparticle cellular uptake was assessed by flow-cytometry scatter-light measurements and microscopy imaging after Prussian blue staining; cytotoxicity was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and colony-forming assays. After a single intravenous injection, in vivo nanoparticle biodistribution and clearance were evaluated in mice by Mn spectrophotometric determination and Prussian blue staining in the liver, kidneys, spleen, and brain at different posttreatment times up to 21 days. The same organs were analyzed for any possible histopathological change. The in vitro study demonstrated dose-dependent nanoparticle uptake and statistically significant cytotoxic effects from a concentration of 50 ?g/mL for the MTT assay and 20 ?g/mL for the colony-forming assay. Significant increases in Mn concentrations were detected in all analyzed organs, peaking at 6 hours after injection and then gradually declining. Clearance appeared complete at 7 days in the kidneys, spleen, and brain, whereas in the liver Mn levels remained statistically higher than in vehicle-treated mice up to 3 weeks postinjection. No evidence of irreversible histopathological damage to any of the tested organs was observed. A comparison of the lowest in vitro toxic concentration with the intravenously injected dose and the administered dose of other ferrofluid drugs currently in clinical practice suggests that there might be sufficient safety margins for further development of our formulation. PMID:24790434

  14. High Valent Manganese and Cobalt Complexes of Oxidatively Robust Nitrogen and Oxygen Donor Ligands.

    NASA Astrophysics Data System (ADS)

    Gordon-Wylie, Scott Wallace

    1995-01-01

    The focus of this thesis is to extend the range of ligands that satisfy the Collins criteria through a program of organic synthesis, and to apply the resulting high valent metal ligand complexes to the solution of current problems in structural inorganic chemistry, solid state chemistry (with a particular emphasis on magnetic interactions in solids) and to homogeneous and heterogeneous catalysis. Notable achievements along these directions to date are: (i) A streamlined synthesis of diamide dialkoxide and diamide diphenoxide acyclic ligands which allows for a wide range of both electron withdrawing and electron donating substituents to be incorporated into the ligand framework. (ii) The first example of a LMn(V)O species stable enough to be crystallographically characterized was obtained, utilizing the acyclic ligands of (i). (iii) Catalytic O-atom transfer oxidations utilizing acyclic ligands from (i) have been performed. Planar Co(III) complexes of these ligands can catalyze O-atom transfers, ^1 with 30-50 turnovers, including enantioselective ones,^2 implicating that the ligands remain at least partially intact during the catalytic process. (iv) Unusual magnetic ordering has been observed in an infinite linear chain of S = 2 LMn(III) centers, in collaboration with Edmund P. Day. (v) Ferromagnetic exchange has been obtained in a ((LCo(III)) _3Co(II)) ^{-} complex^4 Magnetic model building in collaboration with Gordon Yee and Emile Bominaar has led to an understanding of the magnetic data suitable for publication.^5 (vi) Adaptation of a range of electronic substituents (see (i)) into a macrocyclic framework^7 allows for the preparation of hydrolytically and oxidatively stable high valent metal complexes. The presence of a range of electronic substituents further allows redox potentials for a single (LM) ^{rm n+}/(LM) ^{(rm n+1)+ } oxidation process to be tuned over a range that spans ca. 1 V. (vii) Initial linear syntheses for these macrocycles involved the use of organic azide intermediates. (viii) A new macrocyclic switching ligand has been synthesized utilizing (vii), that allows H^{+} or other lewis acids to act at the secondary site as electron withdrawing groups from the metal. In the structurally characterized switching (Co(III)( kappa^4-L)) ^{ -} complex, there is a bidentate switching site consisting of a pyridine-N and an adjacent amide-O donor. It has been found that the cobalt(II) derivative (CO(II)(kappa^4-L)) ^{-} readily reduces O _2 by an outer sphere (presumably by 1 e ^{-}) process. (ix) Robust homogeneous metalloredox-active oxidants are an important strategic goal for primary pollution prevention, or what is often called "green chemistry". Use of (vii) provides access to quantities of a macrocyclic ligand, that is derivatized in such a way that it can be attached to a solid polymer support. (x) C-H bond activation has been observed in iron systems^{15} in collaboration with Mike Bartos (the principal investigator) where use of (vii) has allowed quantities of ligand to be synthesized and burned in reaction chemistry with nitriles and oxidants. (xi) Macrocyclic ligands with organic solubilizing groups have been prepared utilizing (vii) and metal complexes with substantial alkane solubility result. (Abstract shortened by UMI.).

  15. Spinel manganese-nickel-cobalt ternary oxide nanowire array for high-performance electrochemical capacitor applications.

    PubMed

    Li, Lu; Zhang, Yongqi; Shi, Fan; Zhang, Yijun; Zhang, Jiaheng; Gu, Changdong; Wang, Xiuli; Tu, Jiangping

    2014-10-22

    Aligned spinel Mn-Ni-Co ternary oxide (MNCO) nanowires are synthesized by a facile hydrothermal method. As an electrode of supercapacitors, the MNCO nanowire array on nickel foam shows an outstanding specific capacitance of 638 F g(-1) at 1 A g(-1) and excellent cycling stability. This exceptional performance benefits from its nanowire architecture, which can provide large reaction surface area, fast ion and electron transfer, and good structural stability. Furthermore, an asymmetric supercapacitor (ASC) with high energy density is assembled successfully by employing the MNCO nanowire array as positive electrode and carbon black as negative electrode. The excellent electrochemical performances indicate the promising potential application of the ASC device in the energy storage field. PMID:25247606

  16. Synthesis of manganese ferrite/graphene oxide nanocomposites for biomedical applications.

    PubMed

    Peng, Erwin; Choo, Eugene Shi Guang; Chandrasekharan, Prashant; Yang, Chang-Tong; Ding, Jun; Chuang, Kai-Hsiang; Xue, Jun Min

    2012-12-01

    In this study, MnFe(2)O(4) nanoparticle (MFNP)-decorated graphene oxide nanocomposites (MGONCs) are prepared through a simple mini-emulsion and solvent evaporation process. It is demonstrated that the loading of magnetic nanocrystals can be tuned by varying the ratio of graphene oxide/magnetic nanoparticles. On top of that, the hydrodynamic size range of the obtained nanocomposites can be optimized by varying the sonication time during the emulsion process. By fine-tuning the sonication time, MGONCs as small as 56.8 ± 1.1 nm, 55.0 ± 0.6 nm and 56.2 ± 0.4 nm loaded with 6 nm, 11 nm, and 14 nm MFNPs, respectively, are successfully fabricated. In order to improve the colloidal stability of MGONCs in physiological solutions (e.g., phosphate buffered saline or PBS solution), MGONCs are further conjugated with polyethylene glycol (PEG). Heating by exposing MGONCs samples to an alternating magnetic field (AMF) show that the obtained nanocomposites are efficient hyperthermia agents. At concentrations as low as 0.1 mg Fe mL(-1) and under an 59.99 kA m(-1) field, the highest specific absorption rate (SAR) recorded is 1588.83 W g(-1) for MGONCs loaded with 14 nm MFNPs. It is also demonstrated that MGONCs are promising as magnetic resonance imaging (MRI) T(2) contrast agents. A T(2) relaxivity value (r(2) ) as high as 256.2 (mM Fe)(-1) s(-1) could be achieved with MGONCs loaded with 14 nm MFNPs. The cytotoxicity results show that PEGylated MGONCs exhibit an excellent biocompatibility that is suitable for biomedical applications. PMID:22962025

  17. Development and application of 16S rRNA-targeted probes for detection of iron- and manganese-oxidizing sheathed bacteria in environmental samples.

    PubMed Central

    Siering, P L; Ghiorse, W C

    1997-01-01

    Comparative sequence analysis of the 16S rRNA genes from several Leptothrix and Sphaerotilus strains led to the design of an oligonucleotide probe (PS-1) based on a sequence within the hypervariable region 1 specific for four Leptothrix strains and for one of the four Sphaerotilus natans strains examined. Another probe (PSP-6) was based on a sequence within the hypervariable region 2. PSP-6 was specific for one of the two evolutionary lineages previously described for Leptothrix spp. (P. L. Siering and W. C. Ghiorse, Int. J. Syst. Bacteriol. 46:173-182, 1996). Fluorescein-labeled oligonucleotide probes were synthesized, and their specificity for fluorescence in situ hybridization identification was confirmed by a laser scanning microscopy technique (W. C. Ghiorse, D. N. Miller, R. L. Sandoli, and P. L. Siering, Microsc. Res. Tech. 33:73-86, 1996) to compare whole-cell hybridizations of closely related bacteria. Probe specificity was also tested in dot blot against total RNA isolated from four Leptothrix strains, four Sphaerotilus strains, and 15 other members of the class Proteobacteria. When the probes were tested on samples from the Sapsucker Woods wetland habitat where Leptothrix spp. are thought to play a role in manganese and iron oxidation, positive signals were obtained from several sheathed filamentous bacteria including some that were morphologically similar to previously isolated strains of "Leptothrix discophora." Other unknown filamentous sheathed bacteria also gave strong positive signals. This work provides a foundation for future studies correlating the presence of members of the Leptothrix-Sphaerotilus group of sheathed bacteria with manganese and iron oxidation activity in habitats where biological iron and manganese oxidation are important environmental processes. PMID:9023942

  18. Development and application of 16S rRNA-targeted probes for detection of iron- and manganese-oxidizing sheathed bacteria in environmental samples.

    PubMed

    Siering, P L; Ghiorse, W C

    1997-02-01

    Comparative sequence analysis of the 16S rRNA genes from several Leptothrix and Sphaerotilus strains led to the design of an oligonucleotide probe (PS-1) based on a sequence within the hypervariable region 1 specific for four Leptothrix strains and for one of the four Sphaerotilus natans strains examined. Another probe (PSP-6) was based on a sequence within the hypervariable region 2. PSP-6 was specific for one of the two evolutionary lineages previously described for Leptothrix spp. (P. L. Siering and W. C. Ghiorse, Int. J. Syst. Bacteriol. 46:173-182, 1996). Fluorescein-labeled oligonucleotide probes were synthesized, and their specificity for fluorescence in situ hybridization identification was confirmed by a laser scanning microscopy technique (W. C. Ghiorse, D. N. Miller, R. L. Sandoli, and P. L. Siering, Microsc. Res. Tech. 33:73-86, 1996) to compare whole-cell hybridizations of closely related bacteria. Probe specificity was also tested in dot blot against total RNA isolated from four Leptothrix strains, four Sphaerotilus strains, and 15 other members of the class Proteobacteria. When the probes were tested on samples from the Sapsucker Woods wetland habitat where Leptothrix spp. are thought to play a role in manganese and iron oxidation, positive signals were obtained from several sheathed filamentous bacteria including some that were morphologically similar to previously isolated strains of "Leptothrix discophora." Other unknown filamentous sheathed bacteria also gave strong positive signals. This work provides a foundation for future studies correlating the presence of members of the Leptothrix-Sphaerotilus group of sheathed bacteria with manganese and iron oxidation activity in habitats where biological iron and manganese oxidation are important environmental processes. PMID:9023942

  19. Molecular Structure of Quartz

    NSDL National Science Digital Library

    2002-08-26

    Quartz has been known since ancient times. It was referred to as krystallos by the Greeks, but this later became the generic term for crystal. The name quartz is derived from the German quarz (c. 1530 A.D.). Although quartz occurs in almost every geological environment including the United States, the U.S. is 100% import reliant on industrial quartz. The major import sources for 1997-2000 were Brazil, Germany, and Madagascar. Many varieties of gemstones are quartz, including amethyst, smoky quartz, and rose quartz. One of the uses for electronic-grade quartz crystal is frequency control in radios, televisions, and other electronic communications. Quartz sandstone is used for building and quartz sand is used to make sandpaper.

  20. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    SciTech Connect

    Liang, W.

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S{sub 2} state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S{sub 2} state with the g{approx}4 electron paramagnetic resonance (EPR) signal (S{sub 2}-g4 state) was compared with that in the S{sub 2} state with multiline signal (S{sub 2}-MLS state) and the S{sub 1} state. The S{sub 2}-g4 state has a higher XAS inflection point energy than that of the S{sub 1} state, indicating the oxidation of Mn in the advance from the S{sub 1} to the S{sub 2}-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S{sub 2}-g4 state is different from that in the S{sub 2}-MLS or the S{sub 1} state. In the S{sub 2}-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 {angstrom} and 2.85 {angstrom}. Very little distance disorder exists in the second shell of the S{sub 1} or S{sub 2}-MLS states. The third shell of the S{sub 2}-g4 state at about 3.3 {angstrom} also contains increased heterogeneity relative to that of the S{sub 2}-MLS or the S{sub 1} state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct {open_quotes}pure{close_quotes} S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S{sub 1} {yields} S{sub 2} transition.

  1. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide.

    PubMed

    Kuo, Cheng-Chi; Lan, Wen-Jie; Chen, Chun-Hu

    2014-01-01

    High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10(-2) S cm(-1)) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 ?M was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed. PMID:24196690

  2. Surface chemistry of coated lithium manganese nickel oxide thin film cathodes studied by XPS

    SciTech Connect

    Baggetto, Loic [ORNL] [ORNL; Dudney, Nancy J [ORNL] [ORNL; Veith, Gabriel M [ORNL] [ORNL

    2013-01-01

    The effect of coating high voltage LiMn1.5Ni0.5O4 spinel cathode thin films with three metal oxide thin layers is discussed. The changes in surface chemistry of the electrodes are measured by X-ray photoelectron spectroscopy. ZnO is found to decompose during the first charge whereas Al2O3 and ZrO2 are stable for more than 100 cycles. ZrO2, however, importantly limits the available Li storage capacity of the electrochemical reaction due to poorer kinetics. Al2O3 offers the best results in term of capacity retention. Upon cycling, the evidence of a signal at 75.4 eV in the Al2p binding energy spectrum indicates the partial conversion of Al2O3 into Al2O2F2. Moreover, the continuous formation of PEO , esters and LixPOyFz compounds on the surface of the electrodes is found for all coating materials.

  3. Manganese oxide-modified biochars: Preparation, characterization, and sorption of arsenate and lead.

    PubMed

    Wang, Shengsen; Gao, Bin; Li, Yuncong; Mosa, Ahmed; Zimmerman, Andrew R; Ma, Lena Q; Harris, Willie G; Migliaccio, Kati W

    2015-04-01

    This work explored two modification methods to improve biochar's ability to sorb arsenic (As) and lead (Pb). In one, pine wood feedstock was pyrolyzed in the presence of MnCl2·4H2O (MPB) and in the other it was impregnated with birnessite via precipitation following pyrolysis (BPB). The resulting biochars were characterized using thermogravimetry, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analyses. The dominant crystalline forms of Mn oxides in the MPB and BPB were manganosite and birnessite, respectively. Batch sorption studies were carried out to determine the kinetics and magnitude of As(V) and Pb(II) onto the biochars. As(V) and Pb(II) sorption capacities of MPB (0.59 and 4.91g/kg) and BPB (0.91 and 47.05g/kg) were significantly higher than that of the unmodified biochar (0.20 and 2.35g/kg). BPB showed the highest sorption enhancement because of the strong As(V) and Pb(II) affinity of its birnessite particles. PMID:25625462

  4. Reflections on Small Molecule Manganese Models that Seek to Mimic Photosynthetic Water Oxidation Chemistry

    PubMed Central

    Mullins, Christopher S.

    2008-01-01

    Recent advances in the study of the Oxygen Evolving Complex (OEC) of Photosystem II (PSII) include structural information attained from several X-ray crystallographic (XRD) and spectroscopic (XANES and EXAFS) investigations. The possible structural features gleaned from these studies have enabled synthetic chemists to design more accurate model complexes, which in turn, offer better insight into the possible pathways used by PSII to drive photosynthetic water oxidation catalysis. Mononuclear model compounds have been used to advance the knowledge base regarding the physical properties and reactivity of high-valent (MnIV or MnV) complexes. Such investigations have been especially important in regard to the manganyl (MnIV=O or MnV?O) species, as there are no reports, to date, of any structural characterized multinuclear model compounds that incorporate such a functionality. Dinuclear and trinuclear model compounds have also been thoroughly studied in attempts to draw further comparison to the physical properties observed in the natural system and to design systems of catalytic relevance. As the reactive center of the OEC has been shown to contain an oxo-Mn4Ca cluster, exact structural models necessitate a tetranuclear Mn core. The number of models that make use of Mn4 clusters has risen substantially in recent years, and these models have provided evidence to support and refute certain mechanistic proposals. Further work is needed to adequately address the rationale for Ca (and Cl) in the OEC and to determine the sequence of events that lead to O2 evolution. PMID:19081816

  5. Intertwined nanocarbon and manganese oxide hybrid foam for high-energy supercapacitors.

    PubMed

    Wang, Wei; Guo, Shirui; Bozhilov, Krassimir N; Yan, Dong; Ozkan, Mihrimah; Ozkan, Cengiz S

    2013-11-11

    Rapid charging and discharging supercapacitors are promising alternative energy storage systems for applications such as portable electronics and electric vehicles. Integration of pseudocapacitive metal oxides with single-structured materials has received a lot of attention recently due to their superior electrochemical performance. In order to realize high energy-density supercapacitors, a simple and scalable method is developed to fabricate a graphene/MWNT/MnO2 nanowire (GMM) hybrid nanostructured foam, via a two-step process. The 3D few-layer graphene/MWNT (GM) architecture is grown on foamed metal foils (nickel foam) via ambient pressure chemical vapor deposition. Hydrothermally synthesized ?-MnO2 nanowires are conformally coated onto the GM foam by a simple bath deposition. The as-prepared hierarchical GMM foam yields a monographical graphene foam conformally covered with an intertwined, densely packed CNT/MnO2 nanowire nanocomposite network. Symmetrical electrochemical capacitors (ECs) based on GMM foam electrodes show an extended operational voltage window of 1.6 V in aqueous electrolyte. A superior energy density of 391.7 Wh kg(-1) is obtained for the supercapacitor based on the GMM foam, which is much higher than ECs based on GM foam only (39.72 Wh kg(-1) ). A high specific capacitance (1108.79 F g(-1) ) and power density (799.84 kW kg(-1) ) are also achieved. Moreover, the great capacitance retention (97.94%) after 13 000 charge-discharge cycles and high current handability demonstrate the high stability of the electrodes of the supercapacitor. These excellent performances enable the innovative 3D hierarchical GMM foam to serve as EC electrodes, resulting in energy-storage devices with high stability and power density in neutral aqueous electrolyte. PMID:23650047

  6. Laser welding of fused quartz

    DOEpatents

    Piltch, Martin S.; Carpenter, Robert W.; Archer III, McIlwaine

    2003-06-10

    Refractory materials, such as fused quartz plates and rods are welded using a heat source, such as a high power continuous wave carbon dioxide laser. The radiation is optimized through a process of varying the power, the focus, and the feed rates of the laser such that full penetration welds may be accomplished. The process of optimization varies the characteristic wavelengths of the laser until the radiation is almost completely absorbed by the refractory material, thereby leading to a very rapid heating of the material to the melting point. This optimization naturally occurs when a carbon dioxide laser is used to weld quartz. As such this method of quartz welding creates a minimum sized heat-affected zone. Furthermore, the welding apparatus and process requires a ventilation system to carry away the silicon oxides that are produced during the welding process to avoid the deposition of the silicon oxides on the surface of the quartz plates or the contamination of the welds with the silicon oxides.

  7. O-atom transport catalysis by neutral manganese oxide clusters in the gas phase: reactions with CO, C2H4, NO2, and O2.

    PubMed

    Yin, Shi; Wang, Zhechen; Bernstein, Elliot R

    2013-08-28

    Reactions of CO, C2H4, NO2, and O2 with neutral Mn(m)O(n) clusters in a fast flow reactor are investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. Mn(m)O(n) clusters are generated through laser ablation of a manganese target in the presence of 5% O2/He carrier gas. A strong size dependent reactivity of Mn(m)O(n) clusters is characterized. Reactions Mn2O5/Mn3O7 + CO ? Mn2O4/Mn3O6 + CO2 are found for CO oxidation by Mn(m)O(n) clusters, while only association products Mn2O(3-5)C2H4 and Mn3O(5-7)C2H4 are observed for reactions of C2H4 with small Mn(m)O(n) clusters. Reactions of Mn(m)O(n) clusters with NO2 and O2 are also investigated, and the small Mn2O(n) clusters are easily oxidized by NO2. This activation suggests that a catalytic cycle can be generated for the Mn2O5 cluster: Mn2O5 + CO + NO2 ? Mn2O4 + CO2 + NO2 ? Mn2O5 + CO2 + NO. Density functional theory (DFT) calculations are performed to explore the potential energy surfaces for the reactions Mn2O(4,5)/Mn3O7 + CO ? Mn2O(3,4)/Mn3O6 + CO2, Mn2O5 + C2H4 ? Mn2O4 + CH3CHO, and Mn2O4 + NO2 ? Mn2O5 + NO. Barrierless and thermodynamically favorable pathways are obtained for Mn2O5?Mn3O7 + CO and Mn2O4 + NO2 reactions. A catalytic cycle for CO oxidation by NO2 over a manganese oxide surface is proposed based on our experimental and theoretical investigations. The various atom related reaction mechanisms explored by DFT are in good agreement with the experimental results. Condensed phase manganese oxide is suggested to be a good catalyst for low temperature CO oxidation by NO2, especially for an oxygen rich sample. PMID:24006997

  8. O-atom transport catalysis by neutral manganese oxide clusters in the gas phase: Reactions with CO, C2H4, NO2, and O2

    NASA Astrophysics Data System (ADS)

    Yin, Shi; Wang, Zhechen; Bernstein, Elliot R.

    2013-08-01

    Reactions of CO, C2H4, NO2, and O2 with neutral MnmOn clusters in a fast flow reactor are investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. MnmOn clusters are generated through laser ablation of a manganese target in the presence of 5% O2/He carrier gas. A strong size dependent reactivity of MnmOn clusters is characterized. Reactions Mn2O5/Mn3O7 + CO ? Mn2O4/Mn3O6 + CO2 are found for CO oxidation by MnmOn clusters, while only association products Mn2O3-5C2H4 and Mn3O5-7C2H4 are observed for reactions of C2H4 with small MnmOn clusters. Reactions of MnmOn clusters with NO2 and O2 are also investigated, and the small Mn2On clusters are easily oxidized by NO2. This activation suggests that a catalytic cycle can be generated for the Mn2O5 cluster: Mn2O5 + CO + NO2 ? Mn2O4 + CO2 + NO2 ? Mn2O5 + CO2 + NO. Density functional theory (DFT) calculations are performed to explore the potential energy surfaces for the reactions Mn2O4,5/Mn3O7 + CO ? Mn2O3,4/Mn3O6 + CO2, Mn2O5 + C2H4 ? Mn2O4 + CH3CHO, and Mn2O4 + NO2 ? Mn2O5 + NO. Barrierless and thermodynamically favorable pathways are obtained for Mn2O5/Mn3O7 + CO and Mn2O4 + NO2 reactions. A catalytic cycle for CO oxidation by NO2 over a manganese oxide surface is proposed based on our experimental and theoretical investigations. The various atom related reaction mechanisms explored by DFT are in good agreement with the experimental results. Condensed phase manganese oxide is suggested to be a good catalyst for low temperature CO oxidation by NO2, especially for an oxygen rich sample.

  9. Porous cobalt-manganese oxide nanocubes derived from metal organic frameworks as a cathode catalyst for rechargeable Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Wang, Liangjun; Xu, Leilei; Ge, Xiaoming; Zhao, Xiao; Lai, Min; Liu, Zhaolin; Chen, Wei

    2014-12-01

    The development of cathode catalysts with a porous structure is essential to design Li-O2 batteries with a high rate performance and good cycle stability. Herein, spinel-type porous cobalt-manganese oxide (Co-Mn-O) nanocubes derived from metal organic frameworks were employed as an electrocatalyst in a Li-O2 battery. The battery with the porous Co-Mn-O nanocubes electrode showed a low overpotential and enhanced capacity. The synergistic effects of large specific surface area, porous structure, and the high electrocatalytic activity of the porous Co-Mn-O nanocubes electrode endowed the Li-O2 battery with a good rate performance and excellent cycle stability up to 100 cycles.The development of cathode catalysts with a porous structure is essential to design Li-O2 batteries with a high rate performance and good cycle stability. Herein, spinel-type porous cobalt-manganese oxide (Co-Mn-O) nanocubes derived from metal organic frameworks were employed as an electrocatalyst in a Li-O2 battery. The battery with the porous Co-Mn-O nanocubes electrode showed a low overpotential and enhanced capacity. The synergistic effects of large specific surface area, porous structure, and the high electrocatalytic activity of the porous Co-Mn-O nanocubes electrode endowed the Li-O2 battery with a good rate performance and excellent cycle stability up to 100 cycles. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05865h

  10. Carbon nanotube-assisted electrodeposition. Part II: Superior pseudo-capacitive behavior of manganese oxide film electrodeposited at high current densities

    NASA Astrophysics Data System (ADS)

    Eftekhari, Ali; Molaei, Foroogh

    2015-01-01

    A practical approach for controlling the morphology and electrochemical properties of electroactive materials is proposed. In this study, manganese oxide films were galvanostatically deposited in the presence of a small amount of carbon nanotube (CNT). The resulting film cannot be considered as a CNT-based nanocomposite, as no CNT is detected by electron microscopy. However, the manganese oxide electrodeposited delivers an excellent pseudo-capacitive behavior to be used as a superior supercapacitor. The samples prepared by applying a current density of 3.0 mA cm-2 showed a specific capacitance of 280 F g-1. As it seems that the capacitance of this electrode is related to the chemisorption of the alkali cation, an extremely high specific capacitance of 434 F g-1 was achieved in a saturated medium of Li electrolyte. This high specific capacitance can be attributed to a bulk process. The presence of carbon nanotubes results in the formation of nanostructured films which provide a better accessibility for capacitive behavior. Although the exact mechanism for this phenomenon is still vague, the presence of carbon nanotubes (probably as a solid charge carrier) close to the electrode surface is apparently responsible for a different pathway for the electrodeposition process.

  11. The role of nano-sized manganese oxides in the oxygen-evolution reactions by manganese complexes: towards a complete picture.

    PubMed

    Najafpour, Mohammad Mahdi; Ho?y?ska, Ma?gorzata; Shamkhali, Amir Nasser; Kazemi, Sayed Habib; Hillier, Warwick; Amini, Emad; Ghaemmaghami, M; Jafarian Sedigh, Davood; Nemati Moghaddam, Atefeh; Mohamadi, Rahim; Zaynalpoor, Sasan; Beckmann, Katrin

    2014-09-14

    Eighteen Mn complexes with N-donor and carboxylate ligands have been synthesized and characterized. Three Mn complexes among them are new and are reported for the first time. The reactions of oxygen evolution in the presence of oxone (2KHSO5·KHSO4·K2SO4) and cerium(iv) ammonium nitrate catalyzed by these complexes are studied and characterized by UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy, membrane-inlet mass spectrometry and electrochemistry. Some of these complexes evolve oxygen in the presence of oxone as a primary oxidant. CO2 and MnO4(-) are other products of these reactions. Based on spectroscopic studies, the true catalysts for oxygen evolution in these reactions are different. We proposed that for the oxygen evolution reactions in the presence of oxone, the true catalysts are both high valent Mn complexes and Mn oxides, but for the reactions in the presence of cerium(iv) ammonium nitrate, the active catalyst is most probably a Mn oxide. PMID:25046248

  12. Quartz pseudomorphs after coesite

    Microsoft Academic Search

    1977-01-01

    Coesite has recently been described as a primary phase in a mantle-derived kyanite eclogite from the Roberts-Victor kimberlite, South Africa. An additional specimen from the same locality contains large polycrystalline aggregates of quartz, resembling the quartz rims on the coesite grains in the first specimen. The characteristic textures of these quartz pseudomorphs after coesite are described to aid in the

  13. Quartz pseudomorphs after coesite

    Microsoft Academic Search

    JosspH R. Srrlyrs

    Coesite has recently been described as a primary phase in a mantle-derived kyanite eclogite from the Roberts-Victor kimberlite, South Africa. An additional specimen from the same locality contains large polycrystalline aggregates of quartz, resembling the quartz rims on the coesite grains in the first specimen. The characteristic textures of these quartz pseudomorphs after coesite are described to aid in the

  14. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Kuo, Cheng-Chi; Lan, Wen-Jie; Chen, Chun-Hu

    2013-12-01

    High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10-2 S cm-1) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 ?M was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed.High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10-2 S cm-1) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 ?M was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03791f

  15. Manganese nodules: thorium-230: protactinium-231 ratios.

    PubMed

    Sackett, W M

    1966-11-01

    The Th(230): Pa(231) activity ratio in 7 of 11 manganese nodules is less than 10.8, the theoretical production ratio of activities in the ocean. This finding indicates difierential accumulation of these nuclides in authigenic deposits of manganese-iron oxide. PMID:17778807

  16. Extraction of manganese from electrolytic manganese residue by bioleaching.

    PubMed

    Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

    2011-01-01

    Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. PMID:21050747

  17. Occupational Exposure to Welding Fume among Welders: Alterations of Manganese, Iron, Zinc, Copper, and Lead in Body Fluids and the Oxidative Stress Status

    PubMed Central

    Li, Guojun Jane; Zhang, Long-Lian; Lu, Ling; Wu, Ping; Zheng, Wei

    2014-01-01

    Welders in this study were selected from a vehicle manufacturer; control subjects were from a nearby food factory. Airborne manganese levels in the breathing zones of welders and controls were 1.45 ± SD1.08 mg/m3 and 0.11 ± 0.07 ?g/m3, respectively. Serum levels of manganese and iron in welders were 4.3-fold and 1.9-fold, respectively, higher than those of controls. Blood lead concentrations in welders increased 2.5-fold, whereas serum zinc levels decreased 1.2-fold, in comparison with controls. Linear regression revealed the lack of associations between blood levels of five metals and welder’s age. Furthermore, welders had erythrocytic superoxide dismutase activity and serum malondialdehyde levels 24% less and 78% higher, respectively, than those of controls. These findings suggest that occupational exposure to welding fumes among welders disturbs the homeostasis of trace elements in systemic circulation and induces oxidative stress. PMID:15091287

  18. High manganese concentrations in rocks at Gale crater, Mars

    E-print Network

    High manganese concentrations in rocks at Gale crater, Mars Nina L. Lanza1 , Woodward W. Fischer2 to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1­2 orders

  19. EFFECT OF MANGANESE ON GROI,IIHOF SPHAEROTILUS

    E-print Network

    Luther, Douglas S.

    l-rrE I TLg EFFECT OF MANGANESE ON GROI,IIHOF SPHAEROTILUS DISCOPHORUS THESIS SUB spontaneously oxidize at physiological pH' whereas manganous manganese does not, the latter has been preferred ln modern studies of the problem. Work by Prav6 (f4) suggested that manganese autotrophy night exist

  20. Correlating cation ordering and voltage fade in a lithium-manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study.

    PubMed

    Mohanty, Debasish; Sefat, Athena S; Li, Jianlin; Meisner, Roberta A; Rondinone, Adam J; Payzant, E Andrew; Abraham, Daniel P; Wood, David L; Daniel, Claus

    2013-11-28

    Structure-electrochemical property correlation is presented for lithium-manganese-rich layered-layered nickel manganese cobalt oxide (LMR-NMC) having composition Li1.2Co0.1Mn0.55Ni0.15O2 (TODA HE5050) in order to examine the possible reasons for voltage fade during short-to-mid-term electrochemical cycling. The Li1.2Co0.1Mn0.55Ni0.15O2 based cathodes were cycled at two different upper cutoff voltages (UCV), 4.2 V and 4.8 V, for 1, 10, and 125 cycles; voltage fade was observed after 10 and 125 cycles only when the UCV was 4.8 V. Magnetic susceptibility and selected-area electron diffraction data showed the presence of cation ordering in the pristine material, which remained after 125 cycles when the UCV was 4.2 V. When cycled at 4.8 V, the magnetic susceptibility results showed the suppression of cation ordering after one cycle; the cation ordering diminished upon further cycling and was not observed after 125 cycles. Selected-area electron diffraction data from oxides oriented towards the [0001] zone axis revealed a decrease in the intensity of cation-ordering reflections after one cycle and an introduction of spinel-type reflections after 10 cycles at 4.8 V; after 125 cycles, only the spinel-type reflections and the fundamental O3 layered oxide reflections were observed. A significant decrease in the effective magnetic moment of the compound after one cycle at 4.8 V indicated the presence of lithium and/or oxygen vacancies; analysis showed a reduction of Mn(4+) (high spin/low spin) in the pristine oxide to Mn(3+) (low spin) after one cycle. The effective magnetic moment was higher after 10 and 125 cycles at 4.8 V, suggesting the presence of Mn(3+) in a high spin state, which is believed to originate from distorted spinel (Li2Mn2O4) and/or spinel (LiMn2O4) compounds. The increase in effective magnetic moments was not observed when the oxide was cycled at 4.2 V, indicating the stability of the structure under these conditions. This study shows that structural rearrangements in the LMR-NMC oxide happen only at higher potentials (4.8 V, for example) and provides evidence of a direct correlation between cation ordering and voltage fade. PMID:24129599

  1. Effects of properties of manganese oxide-impregnated catalysts and flue gas condition on multipollutant control of Hg(0) and NO.

    PubMed

    Chiu, Chun-Hsiang; Hsi, Hsing-Cheng; Lin, Hong-Ping; Chang, Tien-Chin

    2015-06-30

    This research investigated the effects of manganese oxide (MnOx) impregnation on the physical/chemical properties and multi pollutant control effectiveness of Hg(0) and NO using a V2O5-WO3/TiO2-SiO2 selective catalytic reduction (SCR) catalyst. Raw and MnOx-treated SCR samples were bean-shaped nanoparticles with sizes within 10-30nm. Impregnating MnOx of ?5wt% caused limited changes in physical properties of the catalyst. The decrease in surface area when the impregnated MnOx amount was 10wt% may stem from the pore blockage and particle growth or aggregation of the catalyst. Mn(4+) was the main valence state of impregnated MnOx. Apparent crystallinity of MnOx was not observed based on X-ray diffraction. MnOx impregnation enhanced the Hg(0) oxidation and NO/SO2 removal of SCR catalyst. The 5 and 10% MnOx-impregnated samples had the greatest multi pollutant control potentials for Hg(0) oxidation and NO removal; however, the increasing SO2 removal that may be mainly due to SO2-SO3 conversion should be cautioned. HCl and O2 greatly promoted Hg(0) oxidation. SO2 enhanced Hg(0) oxidation at ?200ppm while NO and NH3 consistently inhibited Hg(0) oxidation. Elevating flue gas temperature enhanced Hg(0) oxidation. Overall, MnOx-impregnated catalysts show stable and consistent multi pollutant removal effectiveness under the test conditions. PMID:25748996

  2. Influence of an interlayer on thermoelectric power factor of HMS film on quartz substrate

    NASA Astrophysics Data System (ADS)

    Hou, Q. R.; Gu, B. F.; Chen, Y. B.

    2014-04-01

    The influence of an AlOx oxide or Si interlayer on the thermoelectric power factor of the higher manganese silicide (HMS, MnSiy, y = 1.73-1.75) film deposited on quartz substrate is investigated. The HMS film and the interlayer are prepared on quartz substrate by magnetron sputtering of MnSi2, Al, Si and Si:B (1 at.% B content) targets. It is found that the metallic phase MnSi is present in the semiconducting HMS film without an interlayer, resulting in a lower Seebeck coefficient, 0.160 mV/K, but not a lower electrical resistivity, 0.021 ? ?cm at 683 K. The thermoelectric power factor is only 122 × 10-6 W/mK2 at 683 K. On the other hand, the metallic phase MnSi disappears and the Seebeck coefficient restores to its high value after using the AlOx oxide or Si interlayer. Besides, the electrical resistivity decreases by using the AlOx oxide or Si:B interlayer. The HMS film with an Si:B interlayer has the highest Seebeck coefficient, 0.247 mV/K, and the lowest electrical resistivity, 0.011 ? ?cm, at 683 K. Thus, the thermoelectric power factor is enhanced and can reach 555 × 10-6 W/mK2 at 683 K.

  3. High-performance binder-free supercapacitor electrode by direct growth of cobalt-manganese composite oxide nansostructures on nickel foam

    PubMed Central

    2014-01-01

    A facile approach composed of hydrothermal process and annealing treatment is proposed to directly grow cobalt-manganese composite oxide ((Co,Mn)3O4) nanostructures on three-dimensional (3D) conductive nickel (Ni) foam for a supercapacitor electrode. The as-fabricated porous electrode exhibits excellent rate capability and high specific capacitance of 840.2 F g-1 at the current density of 10 A g-1, and the electrode also shows excellent cycling performance, which retains 102% of its initial discharge capacitance after 7,000 cycles. The fabricated binder-free hierarchical composite electrode with superior electrochemical performance is a promising candidate for high-performance supercapacitors. PMID:25258611

  4. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    PubMed

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl? as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. PMID:24907577

  5. Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, ?-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

    SciTech Connect

    Koretsky, Carla [Western Michigan University] [Western Michigan University

    2013-11-29

    Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatly impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), ?-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2?nH2O). The results show that all of these materials can bind substantial quantities of hexavalent chromium, especially at low pH. Unexpectedly, experiments with the clay minerals kaolinite and montmorillonite suggest that hexavalent chromium may interact with these solids over much longer periods of time than expected. Furthermore, hexavalent chromium may irreversibly bind to these solids, perhaps because of oxidation-reduction reactions occurring on the surfaces of the clay minerals. More work should be done to investigate and quantify these chemical reactions. Experiments conducted with mixtures of goethite, hydrous manganese oxide, hydrous ferric oxide, ?-alumina, montmorillonite and kaolinite demonstrate that it is possible to correctly predict hexavalent chromium binding in the presence of multiple minerals using thermodynamic models derived for the simpler systems. Further, these models suggest that of the six solid considered in this study, goethite is typically the solid to which most of the hexavalent chromium will bind. Experiments completed with organic-rich and organic-poor natural sediments demonstrate that in organic-rich substrates, organic matter is likely to control uptake of the hexavalent chromium. The models derived and tested in this study for hexavalent chromium binding to ?-alumina, hydrous manganese oxide, goethite, hydrous ferric oxide and clay minerals can be used to better predict changes in hexavalent chromium bioavailability and mobility in contaminated sediments and soils.

  6. In situ high-pressure synchrotron X-ray powder diffraction study of tunnel manganese oxide minerals: hollandite, romanechite, and todorokite

    NASA Astrophysics Data System (ADS)

    Hwang, Gil Chan; Post, Jeffrey E.; Lee, Yongjae

    2015-01-01

    In situ high-pressure synchrotron X-ray powder diffraction study of three tunnel manganese oxide minerals (hollandite with 2 × 2 MnO6 octahedra tunnels, romanechite with 2 × 3 tunnels, and todorokite with 3 × 3 tunnels) was performed using a diamond anvil cell and nominally penetrating alcohol and water mixture as a pressure-transmitting medium up to ~8 GPa. Bulk moduli (B 0) calculated using Murnaghan's equation of state are inversely proportional to the size of the tunnel, i.e., 134(4) GPa for hollandite (I2/m), 108(2) GPa for romanechite (C2/m), and 67(5) GPa for todorokite (P2/m). On the other hand, axial compressibilities show different elastic anisotropies depending on the size of the tunnel, i.e., ?0a (a/a 0) = -0.00066(3) GPa-1, ?0b (b/b 0) = 0.00179(8) GPa-1, ?0c (c/c 0) = 0.00637(4) GPa-1 [c > b > a] for hollandite; ?0a (a/a 0) = 0.00485(4) GPa-1, ?0b (b/b 0) = 0.0016(1) GPa-1, ?0c (c/c 0) = 0.00199(8) GPa-1 [a > c > b] for romanechite; and ?0a (a/a 0) = 0.00826(9) GPa-1, ?0b (b/b 0) = 0.0054(1) GPa-1, ?0c (c/c 0) = 0.00081(8) GPa-1 [a > b > c] for todorokite. Overall, the degree of tunnel distortion increases with increasing pressure and correlates with the size of the tunnel, which is evidenced by the gradual increases in the monoclinic ? angles up to 3 GPa of 0.62°, 0.8°, and 1.15° in hollandite, romanechite, and todorokite, respectively. The compression of tunnel manganese oxides is related to the tunnel distortion and the size of the tunnel.

  7. Structural Features of Manganese Precipitating Bacteria

    NASA Astrophysics Data System (ADS)

    Nealson, Kenneth H.; Tebo, Bradley

    1980-06-01

    Studies of biological communities of the past (and their associated activities) are usually dependent upon preservation of fossil material. With bacteria this rarely occurs because of the absence of sufficient fossilizable cellular material. However, some bacteria deposit metabolic products that can, conditions allowing, be preserved indefinitely. In particular, manganese and iron depositing bacteria have the capacity to form preservable microfossils. In order to better understand these microfossils of the past, we have examined present day morphologies of manganese oxidizing bacteria. These bacteria are highly pleomorphic, depending on the growth medium, the age of the culture, and the extent of manganese oxidation. Transmission electron microscopy indicates that manganese may be deposited either intra-or extra-cellularly. The prognosis of the use of morphological information for the interpretation of ancient and modern manganese deposits is discussed.

  8. The Use of the Cre/loxP System to Study Oxidative Stress in Tissue-Specific Manganese Superoxide Dismutase Knockout Models

    PubMed Central

    Marecki, John C.; Parajuli, Nirmala; Crow, John P.

    2014-01-01

    Abstract Significance: Respiring mitochondria are a significant site for reactions involving reactive oxygen and nitrogen species that contribute to irreversible cellular, structural, and functional damage leading to multiple pathological conditions. Manganese superoxide dismutase (MnSOD) is a critical component of the antioxidant system tasked with protecting the oxidant-sensitive mitochondrial compartment from oxidative stress. Since global knockout of MnSOD results in significant cardiac and neuronal damage leading to early postnatal lethality, this approach has limited use for studying the mechanisms of oxidant stress and the development of disease in specific tissues lacking MnSOD. To circumvent this problem, a number of investigators have employed the Cre/loxP system to precisely knockout MnSOD in individual tissues. Recent Advances: Multiple tissue and organ-specific Cre-expressing mice have been generated, which greatly enhance the specificity of MnSOD knockout in tissues and organ systems that were once difficult, if not impossible to study. Critical Issues: Evaluating the contribution of MnSOD deficiency to oxidant-mediated mitochondrial damage requires careful consideration of the promoter system used for creating the tissue-specific knockout animal, in addition to the collection and interpretation of multiple indices of oxidative stress and damage. Future Directions: Expanded use of well-characterized tissue-specific promoter elements and inducible systems to drive the Cre/loxP recombinational events will lead to a spectrum of MnSOD tissue knockout models, and a clearer understanding of the role of MnSOD in preventing mitochondrial dysfunction in human disease. Antioxid. Redox Signal. 20, 1655–1670. PMID:23641945

  9. 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 (e.g., Tanaka et al., 2010, Loges et al., 2012). Our experimental results demonstrate that biogenic organic ligands such as hydroxamate siderophores, may produce solutions with positive Ce anomaly (Bau et al., 2013) and may even counteract the surface oxidation of Ce on Mn (hydr)oxides. References Bau, M., Tepe, N., Mohwinkel, D., 2013. Siderophore-promoted transfer of rare earth elements and iron from volcanic ash into glacial meltwater, river and ocean water. Earth Planet. Sci. Lett. 364, 30-36. Christenson E. A. and Schijf J. (2011) Stability of YREE complexes with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength. Geochim. Cosmochim. Acta 75, 7047-7062. Loges, A., Wagner, T., Barth, M., Bau, M., Göb, S., and Markl, G. 2012. Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction. Geochimica and Cosmochimica Acta 86, 296-317 Ohta A. and Kawabe I. (2001) REE (III) adsorption onto Mn dioxide (delta-MnO2) and Fe oxyhydroxide: Ce(III) oxidation by delta-MnO2. Geochim. Cosmochim. Acta 65, 695-703. Tanaka K., Tani Y., Takahashi Y., Tanimizu M., Suzuki Y., Kozai N. and Ohnuki T. (2010) A specific Ce oxidation process during sorption of rare earth elements on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. Geochim. Cosmochim. Acta 74, 5463-5477.

  10. Concretionary manganese-iron oxides in streams and their usefulness as a sample medium for geochemical prospecting

    USGS Publications Warehouse

    Nowlan, G.A.

    1976-01-01

    Correlation studies of 400 samples of sieved stream sediments and 325 samples of fluvial, concretionary Mn-Fe oxides from Maine resulted in the separation of elements into the following categories: (1) elements not scavenged by Mn-Fe oxides - B, Cr, K, Mg, Rb, Sc, Ti, V, and Zr; (2) elements probably not scavenged by Mn-Fe oxides - Ag, Be, Ca, Ga, La, Sb, and Y; (3) elements scavenged weakly by Mn-Fe oxides - Cu, Mo, Pb, and Sr; (4) elements scavenged strongly by Mn oxides - Ba, Cd, Co, Ni, Tl, and Zn; and (5) elements scavenged strongly by Fe oxides - As and In. Studies of the scavenged elements showed that the deviation from the mean is characteristically greater in oxide samples as compared to sieved sediments from the same locality. However, a significant increase in contrast between anomalous and background localities, when oxides are the sample medium, more than offsets the disadvantage of data scatter. The use of oxides as a sampling medium clearly and significantly accentuates anomalous localities. In general, non-ratioed data on oxides give very nearly the same results as data consisting of scavenged elements ratioed to Mn and Fe. However, ratioed data expand the geographic area of specific anomalies. Cd and Zn consistently show strong correlations with concretionary Mn-Fe oxides, but their concentrations in the oxides do not generally show as much contrast between anomalous and background localities as do Cu, Mo, and Pb. These latter elements are strongly scavenged where rocks are mineralized. ?? 1976.

  11. Dinuclear manganese complexes containing chiral 1,4,7-triazacyclononane-derived ligands and their catalytic potential for the oxidation of olefins, alkanes, and alcohols.

    PubMed

    Romakh, Vladimir B; Therrien, Bruno; Süss-Fink, Georg; Shul'pin, Georgiy B

    2007-02-19

    Five new 1,4,7-triazacyclononane-derived compounds, sodium 3-(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)propionate (Na[LMe2R']) as well as the enantiopure derivatives (S)-1-(2-methylbutyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R''), SS-trans-2,5,8-trimethyl-2,5,8-triazabicyclo[7.4.01,9]tridecane (SS-LBMe3), (S)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R), and (R)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (R-LMe2R), have been synthesized. Reaction of manganese dichloride with the chiral macrocycles S-LMe2R and R-LMe2R in aqueous ethanol gives, upon oxidation with hydrogen peroxide, the brown dinuclear Mn(III)-Mn(IV) complexes which are enantiomers, [Mn2(S-LMe2R)2(mu-O)2]3+ (S,S-1) and [Mn2(R-LMe2R)2(mu-O)2]3+ (R,R-1). The single-crystal X-ray structure analyses of [S,S-1][PF6]3.0.5(CH3)2CO and [R,R-1][PF6]3.0.5(CH3)2CO show both enantiomers to contain Mn(III) and Mn(IV) centers, each of which being coordinated to three nitrogen atoms of a triazacyclononane ligand and each of which being bridged by two oxo and by two chiral hydroxypropyl pendent arms of the macrocycle. The enantiomeric complexes S,S-1 and R,R-1 were found to catalyze the oxidation of olefins, alkanes, and alcohols with hydrogen peroxide. In the epoxidation of indene the enantiomeric excess values attain 13%. The bond selectivities of the oxidation of linear and branched alkanes suggest the crucial step in this process to be the attack of a sterically hindered high-valent manganese-oxo species on the C-H bond. PMID:17243670

  12. The impact of partial manganese superoxide dismutase (SOD2)-deficiency on mitochondrial oxidant stress, DNA fragmentation and liver injury during acetaminophen hepatotoxicity

    SciTech Connect

    Ramachandran, Anup; Lebofsky, Margitta [Department of Pharmacology, Toxicology and Therapeutics, University of Kansas Medical Center, 3901 Rainbow Blvd, MS 1018, Kansas City, KS 66160 (United States); Weinman, Steven A. [Department of Medicine and Microbiology and Immunology, University of Kansas Medical Center, Kansas City, KS 66160 (United States); Jaeschke, Hartmut, E-mail: hjaeschke@kumc.edu [Department of Pharmacology, Toxicology and Therapeutics, University of Kansas Medical Center, 3901 Rainbow Blvd, MS 1018, Kansas City, KS 66160 (United States)

    2011-03-15

    Acetaminophen (APAP) hepatotoxicity is the most frequent cause of acute liver failure in many countries. The mechanism of cell death is initiated by formation of a reactive metabolite that binds to mitochondrial proteins and promotes mitochondrial dysfunction and oxidant stress. Manganese superoxide dismutase (SOD2) is a critical defense enzyme located in the mitochondrial matrix. The objective of this investigation was to evaluate the functional consequences of partial SOD2-deficiency (SOD2+/-) on intracellular signaling mechanisms of necrotic cell death after APAP overdose. Treatment of C57Bl/6J wild type animals with 200 mg/kg APAP resulted in liver injury as indicated by elevated plasma alanine aminotransferase activities (2870 {+-} 180 U/L) and centrilobular necrosis at 6 h. In addition, increased tissue glutathione disulfide (GSSG) levels and GSSG-to-GSH ratios, delayed mitochondrial GSH recovery, and increased mitochondrial protein carbonyls and nitrotyrosine protein adducts indicated mitochondrial oxidant stress. In addition, nuclear DNA fragmentation (TUNEL assay) correlated with translocation of Bax to the mitochondria and release of apoptosis-inducing factor (AIF). Furthermore, activation of c-jun-N-terminal kinase (JNK) was documented by the mitochondrial translocation of phospho-JNK. SOD2+/- mice showed 4-fold higher ALT activities and necrosis, an enhancement of all parameters of the mitochondrial oxidant stress, more AIF release and more extensive DNA fragmentation and more prolonged JNK activation. Conclusions: the impaired defense against mitochondrial superoxide formation in SOD2+/- mice prolongs JNK activation after APAP overdose and consequently further enhances the mitochondrial oxidant stress leading to exaggerated mitochondrial dysfunction, release of intermembrane proteins with nuclear DNA fragmentation and more necrosis.

  13. Inorganic particulates in removal of heavy metal toxic ions IX. Rapid and efficient removal of Hg(II) by hydrous manganese and tin oxides.

    PubMed

    Mishra, Shuddhodan P; Dubey, Som Shankar; Tiwari, Diwakar

    2004-11-01

    Batch studies have been carried out in the removal of Hg(II) from aqueous solutions by using well-synthesized and -characterized hydrous manganese oxide (HMO) and hydrous tin oxide (HTO) employing a radiotracer technique. Results obtained reveal that increased sorptive concentration (10(-8)-10(-2) mol dm(-3)), temperature (298-328 K), and pH (ca. 2.0-10.5) enhance the removal efficiency of these solids. First-order uptake of Hg(II) on HMO and HTO follows the Freundlich adsorption isotherm for entire concentration range. Positive values of DeltaH0 for the uptake process on both solids indicate endothermic uptake and desorption experiments point to irreversible uptake. Radiation stability of the adsorbents has also been assessed using a 300-mCi (Ra-Be) neutron source having an integral neutron flux of 3.85 x 10(6) N cm(-2) s(-1) and associated with a nominal gamma-dose of ca. 1.72 Gy/h. PMID:15380412

  14. Biogeochemical cycling of manganese in Oneida Lake, New York: whole lake studies of manganese

    NASA Technical Reports Server (NTRS)

    Aguilar, C.; Nealson, K. H.

    1998-01-01

    Oneida Lake, New York is a eutrophic freshwater lake known for its abundant manganese nodules and a dynamic manganese cycle. Temporal and spatial distribution of soluble and particulate manganese in the water column of the lake were analyzed over a 3-year period and correlated with other variables such as oxygen, pH, and temperature. Only data from 1988 are shown. Manganese is removed from the water column in the spring via conversion to particulate form and deposited in the bottom sediments. This removal is due to biological factors, as the lake Eh/pH conditions alone can not account for the oxidation of the soluble manganese Mn(II). During the summer months the manganese from microbial reduction moves from the sediments to the water column. In periods of stratification the soluble Mn(II) builds up to concentrations of 20 micromoles or more in the bottom waters. When mixing occurs, the soluble Mn(II) is rapidly removed via oxidation. This cycle occurs more than once during the summer, with each manganese atom probably being used several times for the oxidation of organic carbon. At the end of the fall, whole lake concentrations of manganese stabilize, and remain at about 1 micromole until the following summer, when the cycle begins again. Inputs and outflows from the lake indicate that the active Mn cycle is primarily internal, with a small accumulation each year into ferromanganese nodules located in the oxic zones of the lake.

  15. Quartz Crystal Clocks

    NASA Technical Reports Server (NTRS)

    1976-01-01

    General Time Corporation, under contract to NASA, developed a quartz crystal for obtaining a stable time base from which all mission times could be derived. This later became basis of consumer clocks and watches with accuracy of one minute a year, watches useful in timing sports events as well as general use. When quartz is electrically stimulated it can vibrate millions of times a second. Since timepieces use a vibrating body to keep up time, incredibly fast vibration of a quartz crystal--up to 4,194,304 beats a second opened a new horizon in accuracy.

  16. Manganese porphyrin multilayer films assembled on ITO electrodes via zirconium phosphonate chemistry: chemical and electrochemical

    E-print Network

    Manganese porphyrin multilayer films assembled on ITO electrodes via zirconium phosphonate University, 2145 Sheridan Road, Evanston, IL 60208-3113 A supported manganese porphyrin-based oxidation)porphyrinato] manganese(III) chloride (2) and zirconium(IV) ions on indium­tin oxide electrodes. This assembly technique

  17. Geodynamic and climate controls in the formation of Mio-Pliocene world-class oxidized cobalt and manganese ores in the Katanga province, DR Congo

    NASA Astrophysics Data System (ADS)

    Decrée, Sophie; Deloule, Étienne; Ruffet, Gilles; Dewaele, Stijn; Mees, Florias; Marignac, Christian; Yans, Johan; de Putter, Thierry

    2010-10-01

    The Katanga province, Democratic Republic of Congo, hosts world-class cobalt deposits accounting for ~50% of the world reserves. They originated from sediment-hosted stratiform copper and cobalt sulfide deposits within Neoproterozoic metasedimentary rocks. Heterogenite, the main oxidized cobalt mineral, is concentrated as “cobalt caps” along the top of silicified dolomite inselbergs. The supergene cobalt enrichment process is part of a regional process of residual ore formation that also forms world-class “manganese cap” deposits in western Katanga, i.e., the “black earths” that are exploited by both industrial and artisanal mining. Here, we provide constraints on the genesis and the timing of these deposits. Ar-Ar analyses of oxidized Mn ore and in situ U-Pb SIMS measurements of heterogenite yield Mio-Pliocene ages. The Ar-Ar ages suggest a multi-phase process, starting in the Late Miocene (10-5 Ma), when the metal-rich substratum was exposed to the action of meteoric fluids, due to major regional uplift. Further oxidation took place in the Pliocene (3.7-2.3 Ma) and formed most of the observed deposits under humid conditions: Co- and Mn-caps on metal-rich substrata, and coeval Fe laterites on barren areas. These deposits formed prior to the regional shift toward more arid conditions in Central Africa. Arid conditions still prevailed during the Quaternary and resulted in erosion and valley incision, which dismantled the metal-bearing caps and led to ore accumulation in valleys and along foot slopes.

  18. Oxidation of cyclohexene with tert-butylhydroperoxide and hydrogen peroxide catalyzed by alumina-supported manganese(II) complexes

    Microsoft Academic Search

    M Salavati-Niasari; F Farzaneh; M Ghandi

    2002-01-01

    Alumina-supported Mn(II) complexes with ligands of acetylacetonato (acac), N,N?-ethylenebis(salicylideneiminato) (salen), ethylenediamine (en) and 2,2?-bipyridine (bpy) catalyze the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP) and hydrogen peroxide. Oxidation of cyclohexene with TBHP gave 2-cyclohexene-1-ol, 2-cyclohexene-1-one and 1-(tert-butylperoxy)-2-cyclohexene whereas, oxidation with H2O2 resulted in the formation of cyclohexeneoxide and cyclohexene-1,2-diol. Mn(II) catalysts with the nitrogen donor ligands show significantly higher catalytic activity

  19. Manganous oxide as a seed-pellet additive for controlling manganese deficiency in sugar-beet seedlings

    Microsoft Academic Search

    R. F. Farley; Manganese Mineral

    1980-01-01

    Summary Experiments in the laboratory, glasshouse and field during 1975–78 tested manganous oxide as a seed-pellet additive for controlling deficiency in sugar-beet seedlings. There was no experimental evidence that manganous oxide in the seed pellet was ever harmful to seedling establishment. On the contrary, germination tests in the laboratory and experiments in the glasshouse indicated that, in certain conditions, manganous

  20. Microbanded manganese formations; protoliths in the Franciscan Complex, California

    USGS Publications Warehouse

    Huebner, J. Stephen; Flohr, Marta J.

    1990-01-01

    The Buckeye manganese deposit, 93 km southeast of San Francisco in the California Coast Ranges, preserves a geologic history that provides clues to the origin of numerous lenses of manganese carbonate, oxides, and silicates that occur with interbedded radiolarian chert and metashale of the Franciscan Complex. Compositionally and mineralogically laminated Mn-rich protoliths were deformed and dismembered, in a manner that mimics in smaller scale the deformation of the host complex, and then were incipiently metamorphosed at blueschistfacies conditions. Eight phases occur as almost monomineralic protoliths and mixtures: rhodochrosite, caryopilite, chlorite, gageite, taneyamalite, braunite, hausmannite, and laminated chert (quartz). Braunite, gageite, and some chlorite and caryopilite layers were deposited as gel-like materials; rhodochrosite, most caryopilite, and at least some hausmannite layers as lutites; and the chert as turbidites of radiolarian sand. Some gel-like materials are now preserved as transparent, sensibly isotropic relics of materials that fractured or shattered when deformed, creating curved surfaces. In contrast, the micrites flowed between the fragments of gel-like materials. The orebody and most of its constituent minerals have unusually Mn-rich compositions that are described by the system MnO-SiO2-O2-CO2-H2O. High values of Mn/Fe and U/Th, and low concentrations of Co, Cu, and Ni, distinguish the Buckeye deposit from many high-temperature hydrothermal deposits and hydrogenous or diagenetic manganese and ferromanganese nodules and pavements. This chemical signature suggests that ore deposition was related to fluids from the sediment column and seawater. Tungsten is associated exclusively with gageite, in concentrations as high as 80 parts per million. The source of the manganese is unknown; because basalts do not occur near the deposit, it was probably manganese leached from the sediment column by reducing solutions. Low concentrations of calcium (CaO approximately 0.6 weight percent) suggest that the host sediments formed beneath the carbonate-compensation depth. The most probable cause of the microbanding is changing proportions of chemical fluxes supplied to the sediment-seawater interface. The principal fluxes were biogenic silica from the water column, carbon dioxide from organic matter in the sediment column, O2 and other seawater constituents, and Mn +2-bearing fluid. The presence of Al2O3 and TiO2 (supplied by a detrital flux) in the metashale but not the ore lens suggests rapid ore deposition. Material supply-rate changes were probably due to a complex combination of episodic variations in the hydrothermal flux and periodic flows of radiolarian sand (silica and CO2 fluxes) that may be related to climate variations. The processes that form recent marine hydrothermal mounds may be the same as processes that formed the Buckeye deposit. Features common to both include the presence of Mn-oxyhydroxide crusts (corresponding to the Buckeye orebody), a large Mn/Fe ratio, low abundances of most minor elements, and small size. The most important differences are the absence of rhodochrosite and manganese silicates, interlayered with oxide, and the absence of adjacent chert in the contemporary deposits. These differences may be due to an absence of the debris of siliceous pelagic organisms, which accumulated in the Buckeye paleoenvironment. Periodic turbidity flows of chert-forming radiolarian sand could provide the changes in the fluxes of silica and organic matter necessary to form manganese carbonate and silicates. Turbidity flows of graywacke indicate proximity to an environment with high relief. A possible paleodepositional environment is an oceanic spreading center approaching a continental margin at which subduction occurred.

  1. The pH-dependent long-term stability of an amorphous manganese oxide in smelter-polluted soils: Implication for chemical stabilization of metals and metalloids.

    PubMed

    Ettler, Vojt?ch; Tomášová, Zde?ka; Komárek, Michael; Mihaljevi?, Martin; Šebek, Ond?ej; Michálková, Zuzana

    2015-04-01

    An amorphous manganese oxide (AMO) and a Pb smelter-polluted agricultural soil amended with the AMO and incubated for 2 and 6 months were subjected to a pH-static leaching procedure (pH 3-8) to verify the chemical stabilization effect on metals and metalloids. The AMO stability in pure water was pH-dependent with the highest Mn release at pH 3 (47% dissolved) and the lowest at pH 8 (0.14% dissolved). Secondary rhodochrosite (MnCO3) was formed at the AMO surfaces at pH>5. The AMO dissolved significantly less after 6 months of incubation. Sequential extraction analysis indicated that "labile" fraction of As, Pb and Sb in soil significantly decreased after AMO amendment. The pH-static experiments indicated that no effect on leaching was observed for Cd and Zn after AMO treatments, whereas the leaching of As, Cu, Pb and Sb decreased down to 20%, 35%, 7% and 11% of the control, respectively. The remediation efficiency was more pronounced under acidic conditions and the time of incubation generally led to increased retention of the targeted contaminants. The AMO was found to be a promising agent for the chemical stabilization of polluted soils. PMID:25600581

  2. Novel silver nanoparticle-manganese oxyhydroxide-graphene oxide nanocomposite prepared by modified silver mirror reaction and its application for electrochemical sensing.

    PubMed

    Bai, Wushuang; Nie, Fei; Zheng, Jianbin; Sheng, Qinglin

    2014-04-23

    A gas/liquid interface will be formed when the free volatilized methyl aldehyde gas begins to dissolve in to solution. On the basis of the traditional silver mirror reaction, silver nanoparticle-manganese oxyhydroxide-graphene oxide (Ag-MnOOH-GO) nanocomposite was synthesized at the gas/liquid interface without any protection of inert gas at room temprature. The morphology of the nanocomposites could be controlled by adjusting the reaction temperature and time. The morphology and composition of the nanocomposites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The composites were then applied for electrochemical sensing. The electrochemical investigation for the sensor indicates that it has excellent property to catalyze H2O2, and could detect H2O2 with a low detection limit of 0.2?M and wide linear range of 0.5 ?M to 17.8 mM. The present study provides a general platform for the controlled synthesis of nanomaterials and can be extended to other optical, electronic, and magnetic nanocompounds. PMID:24660983

  3. Controllable synthesis of spinel lithium nickel manganese oxide cathode material with enhanced electrochemical performances through a modified oxalate co-precipitation method

    NASA Astrophysics Data System (ADS)

    Liu, Hongmei; Zhu, Guobin; Zhang, Li; Qu, Qunting; Shen, Ming; Zheng, Honghe

    2015-01-01

    A spinel lithium nickel manganese oxide (LiNi0.5Mn1.5O4) cathode material is synthesized with a modified oxalate co-precipitation method by controlling pH value of the precursor solution and introducing excessive Li source in the precursor. All the samples synthesized through this method are of Fd3m phase with a small amount of P4332 phase. It is found that pH value of the precursor solution considerably affects the morphology, stoichiometry and crystallographic structure of the target material, thereby resulting in different amounts of Mn3+ (i.e., different degree of disorder). 5% excessive Li source in the precursor may compensate for the lithium loss during the high-temperature sintering process and eliminate the LixNi1-xO impurity phase. Under the optimized synthesis conditions, the obtained high-purity LiNi0.5Mn1.5O4 spinel exhibits enhanced electrochemical performances. A reversible capacity of ca. 140 mAh g-1 can be delivered at 0.1C and the electrode retains 106 mAh g-1 at 10C rate. When cycled at 0.2C, a capacity retention of more than 98% is obtained in the initial 50 electrochemical cycles.

  4. Artificial neural network modelling of photodegradation in suspension of manganese doped zinc oxide nanoparticles under visible-light irradiation.

    PubMed

    Abdollahi, Yadollah; Zakaria, Azmi; Sairi, Nor Asrina; Matori, Khamirul Amin; Masoumi, Hamid Reza Fard; Sadrolhosseini, Amir Reza; Jahangirian, Hossein

    2014-01-01

    The artificial neural network (ANN) modeling of m-cresol photodegradation was carried out for determination of the optimum and importance values of the effective variables to achieve the maximum efficiency. The photodegradation was carried out in the suspension of synthesized manganese doped ZnO nanoparticles under visible-light irradiation. The input considered effective variables of the photodegradation were irradiation time, pH, photocatalyst amount, and concentration of m-cresol while the efficiency was the only response as output. The performed experiments were designed into three data sets such as training, testing, and validation that were randomly splitted by the software's option. To obtain the optimum topologies, ANN was trained by quick propagation (QP), Incremental Back Propagation (IBP), Batch Back Propagation (BBP), and Levenberg-Marquardt (LM) algorithms for testing data set. The topologies were determined by the indicator of minimized root mean squared error (RMSE) for each algorithm. According to the indicator, the QP-4-8-1, IBP-4-15-1, BBP-4-6-1, and LM-4-10-1 were selected as the optimized topologies. Among the topologies, QP-4-8-1 has presented the minimum RMSE and absolute average deviation as well as maximum R-squared. Therefore, QP-4-8-1 was selected as final model for validation test and navigation of the process. The model was used for determination of the optimum values of the effective variables by a few three-dimensional plots. The optimum points of the variables were confirmed by further validated experiments. Moreover, the model predicted the relative importance of the variables which showed none of them was neglectable in this work. PMID:25538962

  5. Semi-empirical study of ortho-cresol photo degradation in manganese-doped zinc oxide nanoparticles suspensions

    PubMed Central

    2012-01-01

    The optimization processes of photo degradation are complicated and expensive when it is performed with traditional methods such as one variable at a time. In this research, the condition of ortho-cresol (o-cresol) photo degradation was optimized by using a semi empirical method. First of all, the experiments were designed with four effective factors including irradiation time, pH, photo catalyst’s amount, o-cresol concentration and photo degradation % as response by response surface methodology (RSM). The RSM used central composite design (CCD) method consists of 30 runs to obtain the actual responses. The actual responses were fitted with the second order algebraic polynomial equation to select a model (suggested model). The suggested model was validated by a few numbers of excellent statistical evidences in analysis of variance (ANOVA). The used evidences include high F-value (143.12), very low P-value (<0.0001), non-significant lack of fit, the determination coefficient (R2?=?0.99) and the adequate precision (47.067). To visualize the optimum, the validated model simulated the condition of variables and response (photo degradation %) be using a few number of three dimensional plots (3D). To confirm the model, the optimums were performed in laboratory. The results of performed experiments were quite close to the predicted values. In conclusion, the study indicated that the model is successful to simulate the optimum condition of o-cresol photo degradation under visible-light irradiation by manganese doped ZnO nanoparticles. PMID:22909072

  6. Artificial Neural Network Modelling of Photodegradation in Suspension of Manganese Doped Zinc Oxide Nanoparticles under Visible-Light Irradiation

    PubMed Central

    Abdollahi, Yadollah; Sairi, Nor Asrina; Amin Matori, Khamirul; Fard Masoumi, Hamid Reza

    2014-01-01

    The artificial neural network (ANN) modeling of m-cresol photodegradation was carried out for determination of the optimum and importance values of the effective variables to achieve the maximum efficiency. The photodegradation was carried out in the suspension of synthesized manganese doped ZnO nanoparticles under visible-light irradiation. The input considered effective variables of the photodegradation were irradiation time, pH, photocatalyst amount, and concentration of m-cresol while the efficiency was the only response as output. The performed experiments were designed into three data sets such as training, testing, and validation that were randomly splitted by the software's option. To obtain the optimum topologies, ANN was trained by quick propagation (QP), Incremental Back Propagation (IBP), Batch Back Propagation (BBP), and Levenberg-Marquardt (LM) algorithms for testing data set. The topologies were determined by the indicator of minimized root mean squared error (RMSE) for each algorithm. According to the indicator, the QP-4-8-1, IBP-4-15-1, BBP-4-6-1, and LM-4-10-1 were selected as the optimized topologies. Among the topologies, QP-4-8-1 has presented the minimum RMSE and absolute average deviation as well as maximum R-squared. Therefore, QP-4-8-1 was selected as final model for validation test and navigation of the process. The model was used for determination of the optimum values of the effective variables by a few three-dimensional plots. The optimum points of the variables were confirmed by further validated experiments. Moreover, the model predicted the relative importance of the variables which showed none of them was neglectable in this work. PMID:25538962

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

    PubMed

    Fuller, Christopher C; Bargar, John R

    2014-02-18

    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 (?SXRF) mapping, and chemical extraction. ?SXRF 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. PMID:24460038

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

    PubMed Central

    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 micro-focused Extended X-ray Absorption Fine Structure (EXAFS) and X-ray fluorescence (?SXRF) mapping , bulk EXAFS, and chemical extraction. ?SXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and micro-focused EXAFS spectra of Zn in the biogenic Mn oxides 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 decreasing in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in solid to solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating desorption is not controlled by dissolution of secondary Zn phases. In sum, 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 in Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present. PMID:24460038

  9. Miniature crystalline quartz electronical structure

    Microsoft Academic Search

    L. D. Clayton; E. P. EerNisse; R. W. Ward; R. B. Wiggins

    1989-01-01

    The photolithographic and chemical milling techniques used in fabricating a variety of three-dimensional monocrystalline quartz microstructures are presented. The piezoelectric effect, which is the electromechanical phenomenon utilized in the various applications of quartz technology, is described. Examples of quartz resonators used in sensing applications are presented. These miniature quartz sensors are incorporated into transducer systems which measure pressure, temperature, force,

  10. Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment.

    PubMed

    Loomer, Diana B; Al, Tom A; Banks, Vernon J; Parker, Beth L; Mayer, K Ulrich

    2011-01-25

    The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations. PMID:20889229

  11. Oxidation of cyclohexene with tert-butylhydroperoxide catalyzed by manganese(II) complexes included in zeolite Y

    Microsoft Academic Search

    M Salavati Niassary; F Farzaneh; M Ghandi; L Turkian

    2000-01-01

    Mn(II) complexes with ligands of ethylenediamine, tetramethylethylenediamine, 2,2?-bipyridine, tetramethyl-1,8-naphthalenediamine included in zeolite Y were used for oxidation of cyclohexene with tert-butylhydroperoxide(TBHP) as oxidant in CH2Cl2, CH3OH, C2H5OH, CH3COCH3 and CH3CN. The di(2-cyclohexenyl) ether was identified as the main product. 2-Cyclohexenone and 2-cyclohexene-1-ol were obtained as minor products. It was also found that Mn(bipy)22+-Y in CH3OH and CH3CN had the highest

  12. Postsynthetic functionalization of a hollow silica nanoreactor with manganese oxide-immobilized metal nanocrystals inside the cavity.

    PubMed

    Kim, Soo Min; Jeon, Mina; Kim, Ki Woong; Park, Jaiwook; Lee, In Su

    2013-10-23

    A postsynthetic protocol of functionalizing the preformed hollow nanoparticles with metal nanocrystals was developed based on galvanic replacement reaction on the Mn3O4 surface inside the cavity. The developed protocol produced hollow nanoreactor systems, in which a high density of ultrafine catalytic nanocrystals of a range of noble metals, such as Pd, Pt, Rh, and Ir and their alloys, are dispersively immobilized on an interior surface enclosed by a selectively permeable silica shell. The fabricated hollow nanoreactor exhibited highly enhanced activity, selectivity, and recyclability in catalyzing the oxidation of hydrosilanes, which are attributable to the synergistic combination of the porous silica nanoshell and the oxide-immobilized catalyst system. PMID:24102162

  13. Enhancing catalytic activity by narrowing local energy gaps-x-ray studies of a manganese water oxidation catalyst.

    PubMed

    Xiao, Jie; Khan, Munirah; Singh, Archana; Suljoti, Edlira; Spiccia, Leone; Aziz, Emad F

    2015-03-01

    Changes in the local electronic structure of the Mn?3d orbitals of a Mn catalyst derived from a dinuclear Mn(III) complex during the water oxidation cycle were investigated ex?situ by X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) analyses. Detailed information about the Mn?3d orbitals, especially the local HOMO-LUMO gap on Mn sites revealed by RIXS analyses, indicated that the enhancement in catalytic activity (water oxidation) originated from the narrowing of the local HOMO-LUMO gap when electrical voltage and visible light illumination were applied simultaneously to the Mn catalytic system. PMID:25605663

  14. Manganese-Induced Oxidative DNA Damage in Neuronal SH-SY5Y Cells: Attenuation of thymine base lesions by glutathione and N-acetylcysteine

    PubMed Central

    Stephenson, Adrienne P.; Schneider, Jeffrey A.; Nelson, Bryant C.; Atha, Donald H.; Jain, Ashok; Soliman, Karam F. A.; Aschner, Michael; Mazzio, Elizabeth; Reams, R. Renee

    2013-01-01

    Manganese (Mn) is an essential trace element required for normal function and development. However, exposure to this metal at elevated levels may cause manganism, a progressive neurodegenerative disorder with neurological symptoms similar to idiopathic Parkinson’s disease (IPD). Elevated body burdens of Mn from exposure to parental nutrition, vapors in mines and smelters and welding fumes have been associated with neurological health concerns. The underlying mechanism of Mn neurotoxicity remains unclear. Accordingly, the present study was designed to investigate the toxic effects of Mn2+ in human neuroblastoma SH-SY5Y cells. Mn2+ caused a concentration dependent decrease in SH-SY5Y cellular viability compared to controls. The LD50 value was 12.98 ?M Mn2+ (p <0.001 for control vs. 24h Mn treatment). Both TUNEL and annexin V/propidium iodide apoptosis assays confirmed the induction of apoptosis in the cells following exposure to Mn2+ (2 ?M, 62 ?M or 125 ?M). In addition, Mn2+ induced both the formation and accumulation of DNA single strand breaks (via alkaline comet assay analysis) and oxidatively modified thymine bases (via gas chromatography/mass spectrometry analysis). Pre-incubation of the cells with characteristic antioxidants, either 1 mM N-acetylcysteine or 1 mM glutathione reduced the level of DNA strand breaks and the formation of thymine base lesions, suggesting protection against oxidative cellular damage. Our findings indicate that 1) exposure of SH-SY5Y cells to Mn promotes both the formation and accumulation of oxidative DNA nucleotide base damage, 2) SH-SY5Y cells with accumulated DNA damage are more likely to die via an apoptotic pathway and 3) the accumulated levels of DNA damage can be abrogated by the addition of exogenous chemical antioxidants. This is the first known report of Mn2+-induction and antioxidant protection of thymine lesions in this SH-SY5Y cell line and contributes new information to the potential use of antioxidants as a therapeutic strategy for protection against Mn2+-induced oxidative DNA damage. PMID:23296100

  15. Inhibitory effect of dissolved silica on H?O? decomposition by iron(III) and manganese(IV) oxides: implications for H?O?-based in situ chemical oxidation.

    PubMed

    Pham, Anh Le-Tuan; Doyle, Fiona M; Sedlak, David L

    2012-01-17

    The decomposition of H(2)O(2) on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H(2)O(2), because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand, and montmorillonite that were pre-equilibrated with 0.05-1.5 mM SiO(2) were significantly less reactive toward H(2)O(2) decomposition than their original counterparts, with the H(2)O(2) loss rates inversely proportional to SiO(2) concentrations. In the goethite/H(2)O(2) system, the overall •OH yield, defined as the percentage of decomposed H(2)O(2) producing •OH, was almost halved in the presence of 1.5 mM SiO(2). Dissolved SiO(2) also slowed H(2)O(2) decomposition on manganese(IV) oxide. The presence of dissolved SiO(2) results in greater persistence of H(2)O(2) in groundwater and lower H(2)O(2) utilization efficiency and should be considered in the design of H(2)O(2)-based treatment systems. PMID:22129132

  16. Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

    PubMed Central

    Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

    2011-01-01

    The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

  17. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400?°C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. PMID:25394186

  18. Microbially-mediated thiocyanate oxidation and manganese cycling control arsenic mobility in groundwater at an Australian gold mine

    Microsoft Academic Search

    A. S. Horvath; J. G. Baldisimo; J. W. Moreau

    2010-01-01

    Arsenic contamination of groundwater poses a serious environmental and human health problem in many regions around the world. Historical groundwater chemistry data for a Western-Central Victorian gold mine (Australia) revealed a strong inverse correlation between dissolved thiocyanate and iron(II), supporting the interpretation that oxidation of thiocyanate, a major groundwater contaminant by-product of cyanide-based gold leaching, was coupled to reductive dissolution

  19. Optical contacting of quartz

    NASA Technical Reports Server (NTRS)

    Payne, L. L.

    1982-01-01

    The strength of the bond between optically contacted quartz surfaces was investigated. The Gravity Probe-B (GP-B) experiment to test the theories of general relativity requires extremely precise measurements. The quartz components of the instruments to make these measurements must be held together in a very stable unit. Optical contacting is suggested as a possible method of joining these components. The fundamental forces involved in optical contacting are reviewed and relates calculations of these forces to the results obtained in experiments.

  20. Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

    USGS Publications Warehouse

    Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

    1992-01-01

    Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

  1. COLORIMETRIC DETERMINATION OF MANGANESE

    E-print Network

    Bertsch George F.

    1 COLORIMETRIC DETERMINATION OF MANGANESE (Chemistry 51 Version) The objective of this experiment is to determine the percentage of manganese in a steel sample, using colorimetric methods of analysis. PRINCIPLES This analysis is accomplished by dissolving the steel sample, converting all of the manganese to the intensely

  2. Chronic manganese intoxication

    SciTech Connect

    Huang, C.C.; Chu, N.S.; Lu, C.S.; Wang, J.D.; Tsai, J.L.; Tzeng, J.L.; Wolters, E.C.; Calne, D.B. (Chang Gung Medical College Hospital, Taipei, Taiwan (China))

    1989-10-01

    We report six cases of chronic manganese intoxication in workers at a ferromanganese factory in Taiwan. Diagnosis was confirmed by assessing increased manganese concentrations in the blood, scalp, and pubic hair. In addition, increased manganese levels in the environmental air were established. The patients showed a bradykinetic-rigid syndrome indistinguishable from Parkinson's disease that responded to treatment with levodopa.

  3. Integrin-mediated osteoblastic adhesion on a porous manganese-incorporated TiO2 coating prepared by plasma electrolytic oxidation

    PubMed Central

    ZHANG, ZHENXIANG; GU, BEIBEI; ZHU, WEI; ZHU, LIXIAN

    2013-01-01

    This study was conducted to evaluate the bioactivity of manganese-incorporated TiO2 (Mn-TiO2) coating prepared on titanium (Ti) plate by plasma electrolytic oxidation (PEO) technique in Ca-, P- and Mn-containing electrolytes. The surface topography, phase and element compositions of the coatings were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometry (EDS), respectively. The adhesion of osteoblast-like MG63 cells onto Ti, TiO2 and Mn-TiO2 surfaces was evaluated, and the signal transduction pathway involved was confirmed by the sequential expression of the genes for integrins ?1, ?3, ?1 and ?3, focal adhesion kinase (FAK), and the extracellular regulated kinases (ERKs), including ERK1 and ERK2. The results obtained indicated that Mn was successfully incorporated into the porous nanostructured TiO2 coating, and did not alter the surface topography or the phase composition of the coating. The adhesion of the MG63 cells onto the Mn-incorporated TiO2 coating was significantly enhanced compared with that on the Mn-free TiO2 coating and the pure Ti plates. In addition, the enhanced cell adhesion on the Mn-TiO2 coatings may have been mediated by the binding of the integrin subunits, ?1 and ?1, and the subsequent signal transduction pathway, involving FAK and ERK2. The study indicated that the novel Mn-TiO2 coating has potential for orthopedic implant applications, and that further investigations are required. PMID:24137252

  4. Integrin-mediated osteoblastic adhesion on a porous manganese-incorporated TiO2 coating prepared by plasma electrolytic oxidation.

    PubMed

    Zhang, Zhenxiang; Gu, Beibei; Zhu, Wei; Zhu, Lixian

    2013-09-01

    This study was conducted to evaluate the bioactivity of manganese-incorporated TiO2 (Mn-TiO2) coating prepared on titanium (Ti) plate by plasma electrolytic oxidation (PEO) technique in Ca-, P- and Mn-containing electrolytes. The surface topography, phase and element compositions of the coatings were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometry (EDS), respectively. The adhesion of osteoblast-like MG63 cells onto Ti, TiO2 and Mn-TiO2 surfaces was evaluated, and the signal transduction pathway involved was confirmed by the sequential expression of the genes for integrins ?1, ?3, ?1 and ?3, focal adhesion kinase (FAK), and the extracellular regulated kinases (ERKs), including ERK1 and ERK2. The results obtained indicated that Mn was successfully incorporated into the porous nanostructured TiO2 coating, and did not alter the surface topography or the phase composition of the coating. The adhesion of the MG63 cells onto the Mn-incorporated TiO2 coating was significantly enhanced compared with that on the Mn-free TiO2 coating and the pure Ti plates. In addition, the enhanced cell adhesion on the Mn-TiO2 coatings may have been mediated by the binding of the integrin subunits, ?1 and ?1, and the subsequent signal transduction pathway, involving FAK and ERK2. The study indicated that the novel Mn-TiO2 coating has potential for orthopedic implant applications, and that further investigations are required. PMID:24137252

  5. Copper(II) and lead(II) removal from aqueous solution in fixed-bed columns by manganese oxide coated zeolite.

    PubMed

    Han, Runping; Zou, Weihua; Li, Hongkui; Li, Yanhu; Shi, Jie

    2006-09-21

    The ability of manganese oxide coated zeolite (MOCZ) to adsorb copper and lead ions in single- (non-competitive) and binary- (competitive) component sorption systems was studied in fixed-bed column. The experiments were applied to quantify particle size, bed length, influent flow rate and influent metal concentration on breakthrough time during the removal of copper and lead ions from aqueous solutions using MOCZ column. Results of fixed-bed adsorption showed that the breakthrough time appeared to increase with increase of the bed length and decrease of influent metal concentration, but decreased with increase of the flow rate. The Thomas model was applied to adsorption of copper and lead ions at bed length, MOCZ particle size, different flow rate and different initial concentration to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The model was found suitable for describing the adsorption process of the dynamic behavior of the MOCZ column. The total adsorbed quantities, equilibrium uptakes and total removal percents of Cu(II) and Pb(II) related to the effluent volumes were determined by evaluating the breakthrough curves obtained at different conditions. The results suggested that MOCZ could be used as an adsorbent for an efficient removal of copper and lead ions from aqueous solution. The removal of metal ion was decreased when other additional heavy metal ion was added, but the total saturation capacity of MOCZ for copper and lead ions was not significantly decreased. This competitive adsorption also showed that adsorption of lead ions was decreased insignificantly when copper ions was added to the influent, whereas a dramatic decrease was observed on the adsorption of copper ions by the presence of lead ions. The removal of copper and lead ion by MOCZ columns followed the descending order: Pb(II) > Cu(II). The adsorbed copper and lead ions were easily desorbed from MOCZ with 0.5 mol l(-1) HNO3 solution. PMID:16621258

  6. Adsorption and removal of arsenic (V) using crystalline manganese (II,III) oxide: Kinetics, equilibrium, effect of pH and ionic strength.

    PubMed

    Babaeivelni, Kamel; Khodadoust, Amid P; Bogdan, Dorin

    2014-01-01

    Manganese (II,III) oxide (Mn3O4) crystalline powder was evaluated as a potential sorbent for removal of arsenic (V) from water. Adsorption isotherm experiments were carried out to determine the adsorption capacity using de-ionized (DI) water, a synthetic solution containing bicarbonate alkalinity, and two natual groundwater samples. Adsorption isotherm data followed the Langmuir and Freundlich equations, indicating favorable adsorption of arsenic (V) onto Mn3O4, while results from the Dubinin-Radushkevich equation were suggestive of chemisorption of arsenic (V). When normalized to the sorbent surface area, the maximum adsorption capacity of Mn3O4 for arsenic (V) was 101 ?g m(-2), comparable to that of activated alumina. Arsenic (V) adsorption onto Mn3O4 followed pseudo-second-order kinetics. Adsorption of arsenic (V) was greatest at pH 2, while adsorption at pH 7-9 was within 91% of maximum adsorption, whereas adsorption decreased to 32% of maximum adsorption at pH 10. Surface charge analysis confirmed the adsorption of arsenic (V) onto the acidic surface of the Mn3O4 sorbent with a pHPZC of 7.32. The presence of coexisting ions bicarbonate and phosphate resulted in a decrease in arsenic (V) uptake. Comparable adsorption capacities were obtained for the synthetic solution and both groundwater samples. Overall, crystalline Mn3O4 was an effective and viable sorbent for removal of arsenic (V) from natural water, removing greater than 95% of arsenic (V) from a 1 mg L(-1) solution within 60 min of contact time. PMID:25137534

  7. Mechanical deformation of quartz

    Microsoft Academic Search

    R. D. Baéta; K. H. G. Ashbee

    1970-01-01

    Studies of stress relaxation in plastically deformed synthetic quartz crystals are reported. The calculated activation volumes range between b and 10b , where b is the modulus of the Burgers vector of the slip dislocations. For the same conditions of testing, the measured activation volumes for slip involving either of the Burgers vectors a or c are identical; relatively smaller

  8. Manganese accumulation in soil and plants along Utah roadways: A possible indication of motor vehicle exhaust pollution

    SciTech Connect

    Lytle, C.M.; Smith, B.N.; McKinnon, C.Z. [Brigham Young Univ., Provo, UT (United States)

    1995-06-01

    An organic manganese compound is currently added to gasoline to replace tetraethyl lead as an antiknock fuel additive in the U.S. and Canada. Combustion exhaust gases contain manganese oxides. Manganese oxides are known to cause various deleterious health effects in experimental animals and humans. A field survey of roadside soil and plants in central Utah revealed that soil manganese concentrations in high traffic areas were up to 100-fold higher than historic lead levels. Soil manganese concentrations were highly correlated with distance from the roadway. In addition, roadside aquatic plants were higher in leaf tissue manganese than herbs or grasses. Submerged and emergent aquatic plants were sensitive bioindicators of manganese contamination. Manganese concentrations in soil and in some plant species along impacted roadsides often exceeded levels known to cause toxicity. We conclude that roadside soil and plants were apparently contaminated by manganese oxides from Mn-containing motor vehicle exhaust.

  9. Respective role of Fe and Mn oxide contents for arsenic sorption in iron and manganese binary oxide: an X-ray absorption spectroscopy investigation.

    PubMed

    Zhang, Gaosheng; Liu, Fudong; Liu, Huijuan; Qu, Jiuhui; Liu, Ruiping

    2014-09-01

    In our previous studies, a synthesized Fe-Mn binary oxide was found to be very effective for both As(V) and As(III) removal in aqueous phase, because As(III) could be easily oxidized to As(V). As(III) oxidation and As(V) sorption by the Fe-Mn binary oxide may also play an important role in the natural cycling of As, because of its common occurrence in the environment. In the present study, the respective role of Fe and Mn contents present in the Fe-Mn binary oxide on As(III) removal was investigated via a direct in situ determination of arsenic speciation using X-ray absorption spectroscopy. X-ray absorption near edge structure results indicate that Mn atoms exist in a mixed valence state of +3 and +4 and further confirm that MnOx (1.5 < x < 2) content is mainly responsible for oxidizing As(III) to As(V) through a two-step pathway [reduction of Mn(IV) to Mn(III) and subsequent Mn(III) to Mn(II)] and FeOOH content is dominant for adsorbing the formed As(V). No significant As(III) oxidation by pure FeOOH had been observed during its sorption, when the system was exposed to air. The extended X-ray absorption fine structure results reveal that the As surface complex on both the As(V)- and As(III)-treated sample surfaces is an inner-sphere bidentate binuclear corner-sharing complex with an As-M (M = Fe or Mn) interatomic distance of 3.22-3.24 Å. In addition, the MnOx and FeOOH contents exist only as a mixture, and no solid solution is formed. Because of its high effectiveness, low cost, and environmental friendliness, the Fe-Mn binary oxide would play a beneficial role as both an efficient oxidant of As(III) and a sorbent for As(V) in drinking water treatment and environmental remediation. PMID:25093452

  10. Screening strategy to avoid toxicological hazards of inhaled nanoparticles for drug delivery: The use of a-quartz and nano zinc oxide particles as benchmark

    NASA Astrophysics Data System (ADS)

    Beyerle, Andrea; Schulz, Holger; Kissel, Thomas; Stoeger, Tobias

    2009-02-01

    Nanotechnology is a broad, revolutionary field with promising advantages for new medicine. In this context the rapid development and improvement of so called nanocarriers is of high pharmaceutical interest and some devices are already on the market. In our project we aim to develop well characterized nanoscaled drug delivery systems for an inhalative application. To this end, we focus on the most adverse side-effects within the lung, the cytotoxic and the proinflammatory responses to these nanoparticles (NPs). Before performing any animal experiments, we start with an in vitro screening for analyzing the cytotoxic and proinflammatory effects of the investigated particles on two murine lung target cell lines, the alveolar epithelial like typ II cell line (LA4) and the alveolar macrophage cell line (MH-S). Three different endpoints were estimated, (i) cellular metabolic activity, determined by the WST-1 assay, (ii) membrane integrity, by detection of LDH release and hemolytic activity, and (iii) secretion of inflammatory mediators. To analyze the relative particle toxicity we choose two reference particles as benchmarks, (i) fine a-quartz, and (ii) ultrafine ZnO particles. The investigation of dose-response and kinetics of proinflammatory and toxic effects caused to the named cell lines provide an insight to a close evaluation of our cell based screening strategy. oc-quartz is well known for its inflammatory and toxic potential caused by inhalation, and nanosized ZnO particles - used in a broad field of nanotechnology like electronics, but also cosmetics and pharmaceuticals - is to a high degree cytotoxic and proinflammatory in vitro. Preliminary experiments indicated not only particle and cell specific inflammatory responses, but also different susceptibilities of the cell types being exposed to our benchmark particles regarding their size and surface activities. Exposure to the ?m-sized a-quartz particles affected the viability of epithelia cells less than that of macrophages, pointing to the impact of particle uptake by phagocytosis. In contrast, the nanosized ZnO particles caused much stronger decrease in cell viability and higher levels of LDH in the macrophage cell line compared to epithelial cells, even though the hemolytic activity was much higher for the a-quartz particles than for the nanosized ZnO. For the proinflammatory effects, we observed a clear dose-dependent release of acute phase cytokines (TNF-?, IL-6, G-CSF> CXCL10>CCL2) for both alveolar cell lines after Min-U-Sil exposure. After ZnO treatment the cytokine responses were negligible compare to control cells. In conclusion, our data attach value to the use of different cell types to detect different pathways of toxicity generated by different particle properties. Therefore, we will establish both lung target cell lines for an in vitro screening to analyze proinflammatory and cytotoxicity effects of nanocarriers. The implementation of the two reference particles facilitate the validated classification of the cytotoxic responses caused by the NPs investigated.

  11. Effect of manganese doping on Li-ion intercalation properties of V2O5 films D. M. Yu,ab

    E-print Network

    Cao, Guozhong

    Effect of manganese doping on Li-ion intercalation properties of V2O5 films D. M. Yu,ab S. T. Zhang, such as vanadium oxides, the tunnel compounds of manganese oxides, and transition metal phosphates (e

  12. Manganese biofouling and the corrosion behavior of stainless steel

    Microsoft Academic Search

    W. H. Dickinson; Z. Lewandowski

    1996-01-01

    Manganese? and iron?oxidizing bacteria (MFOB) are widely implicated in microbially influenced corrosion, often in association with sulfate?reducing bacteria (SRB). Traditionally MFOB have been assigned a passive role in the corrosion process, promoting differential aeration cells, and providing oxygen depleted conditions conducive to the growth and corrosive attack of SRB. Recent work, summarized in this article, demonstrates that manganese biofouling alters

  13. Electrochemical catalysis of styrene epoxidation with films of manganese dioxide nanoparticles, and, Synthesis of mixed metal oxides using ultrasonic nozzle spray and microwaves

    NASA Astrophysics Data System (ADS)

    Espinal, Laura

    Films of polyions and octahedral layered manganese oxide (OL-1) nanoparticles on carbon electrodes made by layer-by-layer alternate electrostatic adsorption were active for electrochemical catalysis of styrene epoxidation in solution in the presence of hydrogen peroxide and oxygen. The highest catalytic turnover was obtained by using applied voltage -0.6 V vs. SCE, O2, and 100 mM H2O2. 18O isotope labeling experiments suggested oxygen incorporation from three different sources: molecular oxygen, hydrogen peroxide and/or lattice oxygen from OL-1 depending on the potential applied and the oxygen and hydrogen peroxide concentrations. Oxygen and hydrogen peroxide activate the OL-1 catalyst for the epoxidation. The pathway for styrene epoxidation in the highest yields required oxygen, hydrogen peroxide and a reducing voltage, and may involve an activated oxygen species in the OL-1 matrix. Multicomponent metal oxide (MMO) crystallites were prepared by spraying a reactant solution into a receiving solution or air under microwave radiation at atmospheric pressure. The injection of nitric acid solution through an ultrasonic nozzle into a receiving solution of metal precursor and the use of microwave radiation were combined to form a novel preparation technique called the nozzle-spray/microwave (NMW) method. The inclusion of an additional step, the in situ mixing of precursor solutions prior to their injection through the ultrasonic nozzle spray, led to another procedure called the in situ/nozzle-spray/microwave (INM) method. For comparison, MMO materials with the same metal constituents as those prepared by our novel techniques were prepared by conventional hydrothermal (CH) methods. Fresh materials prepared by NMW, INM and CH methods were heat treated to study the effect of calcination. All materials were characterized before and after calcination using XRD, SEM, Bet, and ICP. The NMW method produces particles with rod-like morphologies different from those obtained using CH methods. The INM method produces an amorphous material that crystallizes after calcination into small (˜200 nm) particles with interesting morphologies. Notably, calcination of materials prepared by both NMW and INM reduces particle size and increases surface area. The present work paves the way to use NMW and INM to prepare MMOs with unique morphologies.

  14. Nanolayered manganese oxide/poly(4-vinylpyridine) as a biomimetic and very efficient water oxidizing catalyst: toward an artificial enzyme in artificial photosynthesis.

    PubMed

    Najafpour, Mohammad Mahdi; Haghighi, Behzad; Ghobadi, Mohadeseh Zarei; Sedigh, Davood Jafarian

    2013-10-01

    Nanolayered Mn oxide/poly(4-vinylpyridine) as a model for Mn cluster in photosystem II was synthesized and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and UV-Visible spectroscopy (UV-Vis). The compound is a very efficient water oxidizing catalyst, and sizable oxygen evolution was detected at 50 mV overpotential at near neutral pH. The number is as low as the overpotential is used by nature in photosystem II of cyanobacteria, algae and green plants for similar reactions. PMID:23959144

  15. ROLE OF MANGANESE REDUCTION/OXIDATION (REDOX) ON FOAMING AND MELT RATE IN HIGH LEVEL WASTE (HLW) MELTERS (U)

    SciTech Connect

    Jantzen, C; Michael Stone, M

    2007-03-30

    High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass and liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn{sub 2}O{sub 3} species to MnO during melter preprocessing. At the lower redox limit of Fe{sup +2}/{summation}Fe {approx} 0.09 about 99% of the Mn{sup +4}/Mn{sup +3} is converted to Mn{sup +2}. Therefore, the lower REDOX limits eliminates melter foaming from deoxygenation.

  16. Factors Affecting the Enhancement of Oxidative Stress Tolerance in Transgenic Tobacco Overexpressing Manganese Superoxide Dismutase in the Chloroplasts.

    PubMed Central

    Slooten, L.; Capiau, K.; Van Camp, W.; Van Montagu, M.; Sybesma, C.; Inze, D.

    1995-01-01

    Two varieties of tobacco (Nicotiana tabacum var PBD6 and var SR1) were used to generate transgenic lines overexpressing Mn-superoxide dismutase (MnSOD) in the chloroplasts. The overexpressed MnSOD suppresses the activity of those SODs (endogenous MnSOD and chloroplastic and cytosolic Cu/ZnSOD) that are prominent in young leaves but disappear largely or completely during aging of the leaves. The transgenic and control plants were grown at different light intensities and were then assayed for oxygen radical stress tolerance in leaf disc assays and for abundance of antioxidant enzymes and substrates in leaves. Transgenic plants had an enhanced resistance to methylviologen (MV), compared with control plants, only after growth at high light intensities. In both varieties the activities of FeSOD, ascorbate peroxidase, dehydroascorbate reductase, and monodehydroascorbate reductase and the concentrations of glutathione and ascorbate (all expressed on a chlorophyll basis) increased with increasing light intensity during growth. Most of these components were correlated with MV tolerance. It is argued that SOD overexpression leads to enhancement of the tolerance to MV-dependent oxidative stress only if one or more of these components is also present at high levels. Furthermore, the results suggest that in var SR1 the overexpressed MnSOD enhances primarily the stromal antioxidant system. PMID:12228398

  17. Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2

    NASA Astrophysics Data System (ADS)

    Oishi, Masatsugu; Yogi, Chihiro; Watanabe, Iwao; Ohta, Toshiaki; Orikasa, Yuki; Uchimoto, Yoshiharu; Ogumi, Zempachi

    2015-02-01

    The reversible redox reaction of oxygen ion was directly observed by soft X-ray absorption spectroscopy for Li1.16Ni0.15Co0.19Mn0.50O2, the Li-rich manganese layered oxide. The O K-edge spectra indicated that a peroxide phase (namely the formation of O22-) appeared and disappeared reversibly by charging and discharging. It was simultaneously observed both in the total electron yield mode and in the partial fluorescence X-ray yield mode, indicating that the peroxide phase exists stably in the crystalline network. These species should play an important role in the high capacity positive electrode.

  18. Nanofabricated quartz cylinders for angular

    E-print Network

    Wang, Michelle

    Nanofabricated quartz cylinders for angular trapping: DNA supercoiling torque detection Christopher nanofabricated quartz cylinders well suited for torque application and detection in an angular optical trap. We that nanofabricated quartz cylinders, when used with an angular trapping instrument, allow direct and simultaneous

  19. Stable Isotope Fractionation during Cr(III) oxidation by manganese oxides Swati Joshi (sjoshi@calstatela.edu), Wang D T (dtw@mit.edu), Ellis A S (aellis3@calstatela.edu) Johnson T M (tmjohnsn@uius.edu), Bullen T D (tdbullen@usgs.gov)

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    Cr stable isotope ratios are being used to monitor Cr redox reactions and associated environmental applications. Previous studies have shown that isotope fractionation (expressed as ?53Cr in the remaining reactant Cr(VI) pool) during Cr(VI) reduction ranges from -1.8% to -4.2 % depending on the reducing agent and processes. A few studies have also been put forth for Cr isotope fractionation during oxidation reactions but mechanisms of isotope fractionation during the oxidation process are not well understood. Oxidation of Cr(III) by pyrolusite (?-MnO2) results in Cr(VI) enriched in 53Cr by +1.1%. We present here a summary of the Cr isotope fractionation during the Cr(III) to Cr(VI) oxidation process using different manganese oxides with recent data from oxidation caused by birnessite and manganite. Both birnessite (?-MnO2) and manganite (MnOOH) are considered common secondary forms of manganese oxides. Manganite is often associated with pyrolusite and some studies have also noted the reductive transformation of birnessite to manganite. Experiments with birnessite and manganite are conducted under varying pH (4 to 6), temperature (4oC and 22oC) and concentration of Cr(III) (10 to 50 mg/L) and Mn-oxides (100 to 500 mg/L). During Cr(III) oxidation with birnessite, we observed ?53Cr of the Cr(VI) product ranging from -0.5% to -0.07%. These results differ markedly from those obtained from oxidation with pyrolusite. Here, during oxidation with birnessite, the final Cr(VI) product is depleted in the heavier isotopes, while oxidation with pyrolusite produces Cr(VI) enriched in the heavier isotopes. We attribute these differences to different rates and isotope fractionations associated with the multi-step electron exchange mechanism and to structural differences between the manganese oxides. Cr(III) oxidation on manganite is generally similar to both pyrolusite and birnessite but the different structure and mixed oxidation state of Mn may result in isotope fractionations that are different from the previous form of Mn-oxides examined. The variations in Cr isotope fractionations seen with the different oxidation mechanisms are critical in interpreting Cr stable isotopes where oxidation reactions mobilize Cr.

  20. Induction of oxidative stress and inflammatory cytokines by manganese chloride in cultured T98G cells, human brain glioblastoma cell line.

    PubMed

    Park, Eun-Jung; Park, Kwangsik

    2010-03-01

    Manganese, an essential trace nutrient in human beings, has been widely used in the steel industry to improve hardness, stiffness, and strength. With the increased applications of manganese compounds, discharge into the environment has rapidly increased and may exert adverse effects on human health. In this study, manganese toxicity was investigated using cultured T98G cells, which are derived from human glioblasts with the ability to differentiate into several different types of neuroglia. Cytotoxicity was shown in manganese-treated groups (100, 200, 400, and 800microM of MnCl(2)), and cell viability was decreased to 58.8% of the control group at 2days after treatment with 800microM of MnCl(2). When cells were treated with manganese for 24h, ROS dose-dependently increased while antioxidant intracellular GSH decreased. With the generation of ROS, the increased activity of caspase-3 was shown, and was followed by chromatin condensation and breakage, which is an indication of the cellular apoptotic process. ROS also triggered pro-inflammatory responses in cultured T98G cells, which were demonstrated by the increased gene expression and protein levels of IL-6 and IL-8. PMID:19815061