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Sample records for oxidation reduction potential

  1. OXIDATION-REDUCTION POTENTIAL MEASUREMENTS OF IMPORTANT OXIDANTS IN DRINKING WATER

    EPA Science Inventory

    Oxidation-reduction (redox) reactions are important in drinking water treatment and distribution. Oxidation-reduction potential (ORP) measurements of water reflect the tendency of major constituents in the water to accept or lose electrons. Although ORP measurements are valuable...

  2. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION POTENTIAL, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  3. Iron oxide reduction in deep Baltic Sea sediments: the potential role of anaerobic oxidation of methane

    NASA Astrophysics Data System (ADS)

    Egger, Matthias; Slomp, Caroline P.; Dijkstra, Nikki; Sapart, Célia J.; Risgaard-Petersen, Nils; Kasten, Sabine; Riedinger, Natascha; Barker Jørgensen, Bo

    2015-04-01

    Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. However, recent studies have shown that AOM may also be coupled to the reduction of iron (Fe) oxides (Beal et al., 2009; Riedinger et al., 2014; Egger et al., 2014). In the Baltic Sea, the transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) ca. 9-7 ka ago (Zillén et al., 2008) resulted in the accumulation of methanogenic brackish/marine sediments overlying Fe-oxide rich lacustrine deposits. The downward diffusion of methane from the brackish/marine sediments into the lake sediments leads to an ideal diagenetic system to study a potential coupling between Fe oxide reduction and methane oxidation. Here, we use porewater and sediment geochemical data obtained at sites M0063 and M0065 during the IODP Baltic Sea Paleoenvironment Expedition 347 in 2013 to identify the potential mechanisms responsible for the apparent Fe oxide reduction in the non-sulfidic limnic sediments below the A/L transition. In this presentation, we will review the various explanations for the elevated ferrous Fe in the porewater in the lake sediments and we will specifically address the potential role of the reaction of methane with Fe-oxides. References: Beal E. J., House C. H. and Orphan V. J. (2009) Manganese- and iron-dependent marine methane oxidation. Science 325, 184-187. Egger M., Rasigraf O., Sapart C. J., Jilbert T., Jetten M. S. M., Röckmann T., van der Veen C., Banda N., Kartal B., Ettwig K. F. and Slomp C. P. (2014) Iron-mediated anaerobic oxidation of methane in brackish coastal sediments. Environ. Sci. Technol. 49, 277-283. Riedinger N., Formolo M. J., Lyons T. W., Henkel S., Beck A. and Kasten S. (2014) An inorganic geochemical argument for coupled anaerobic oxidation of

  4. ANAEROBIC DDT BIOTRANSFORMATION: ENHANCEMENT BY APPLICATION OF SURFACTANTS AND LOW OXIDATION REDUCTION POTENTIAL

    EPA Science Inventory

    Enhancement of anaerobic DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane) biotransformation by mixed cultures was studied with application of surfactants and oxidation reduction potential reducing agents. Without amendments, DDT transformation resulted mainly in the pr...

  5. Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

    PubMed

    Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

    2015-11-01

    Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

  6. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    PubMed

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  7. Changes in oxidation-reduction potential during milk fermentation by wild lactic acid bacteria.

    PubMed

    Morandi, Stefano; Silvetti, Tiziana; Tamburini, Alberto; Brasca, Milena

    2016-08-01

    Oxidation-reduction potential (E h) is a fundamental physicochemical property of lactic acid bacteria that determines the microenvironment during the cheese manufacture and ripening. For this reason the E h is of growing interest in dairy research and the dairy industry. The objective of the study was to perform a comprehensive study on the reduction activity of wild lactic acid bacteria strains collected in different periods (from 1960 to 2012) from Italian dairy products. A total of 709 strains belonging to Lactococcus lactis, Enterococcus durans, E. faecium, E. faecalis and Streptococcus thermophilus species were studied for their reduction activity in milk. Kinetics of milk reduction were characterised by the minimum redox potential (E h7) and time of reaching E h7 (t min), the maximum difference between two measures (Δmax) and the time at which these maximum differences occurred (t*). Broad diversity in kinetic parameters was observed at both species and strain levels. E. faecalis and L. lactis resulted to be the most reducing species, while S. thermophilus was characterised by the lowest reducing power while the greatest heterogeneity was pointed out among E. durans and E. faecium strains. Considering the period of collection (1960-2012) we observed that the more recently isolated strains generally showed less reducing activity. This trend was particularly evident for the species E. durans, E. faecium and L. lactis while an opposite trend was observed in E. faecalis species. Data reported in this research provide new information for a deeper understanding of redox potential changes during milk fermentation due to bacterial growth. Gain knowledge of the redox potential of the LAB cultures could allow a better control and standardisation of cheesemaking process. PMID:27600976

  8. Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)

    USGS Publications Warehouse

    Nordstrom, Darrell Kirk; Wilde, Franceska D.

    2005-01-01

    Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included.

  9. High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    SciTech Connect

    Gerken, James B.; Stahl, Shannon S.

    2015-07-15

    Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  10. Analysis of flow decay potential on Galileo. [oxidizer flow rate reduction by iron nitrate precipitates

    NASA Technical Reports Server (NTRS)

    Cole, T. W.; Frisbee, R. H.; Yavrouian, A. H.

    1987-01-01

    The risks posed to the NASA's Galileo spacecraft by the oxidizer flow decay during its extended mission to Jupiter is discussed. The Galileo spacecraft will use nitrogen tetroxide (NTO)/monomethyl hydrazine bipropellant system with one large engine thrust-rated at a nominal 400 N, and 12 smaller engines each thrust-rated at a nominal 10 N. These smaller thrusters, because of their small valve inlet filters and small injector ports, are especially vulnerable to clogging by iron nitrate precipitates formed by NTO-wetted stainless steel components. To quantify the corrosion rates and solubility levels which will be seen during the Galileo mission, corrosion and solubility testing experiments were performed with simulated Galileo materials, propellants, and environments. The results show the potential benefits of propellant sieving in terms of iron and water impurity reduction.

  11. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  12. Effect of voltage polarity on oxidation-reduction potential by plasma in water

    SciTech Connect

    Miyahara, Takashi; Oizumi, Masanobu; Nakatani, Tatsuyuki; Sato, Takehiko

    2014-04-15

    Use of plasma in water for water treatment and medical treatment is growing and raises expectations of finding advanced functions such as an increase of biological compatibility. In the present study with a focus on the variation of oxidation-reduction potential (ORP), relationships between the electrode polarities of plasma in water and the change of water quality such as conductivity, H{sub 2}O{sub 2} concentration, dissolved hydrogen concentration, pH and ORP were revealed. Similar line spectra of radiation at the electrode tip were observed for each case of positive and negative electrode polarity. The emission intensities of OH (309 nm), Hα (656 nm), and OI (777 nm) for the positive discharge were significantly higher than those for the negative one, though the energy consumption during the discharge period of both cases was nearly the same. Positive electrode polarity was found to be more suitable than negative electrode polarity for increasing dissolved hydrogen gas and hydrogen peroxide. The ORP for the positive polarity decreased from 460 to 45 mV and that for the negative polarity decreased from 460 to 183 mV, although the pH and conductivity were not significantly changed.

  13. Effect of voltage polarity on oxidation-reduction potential by plasma in water

    NASA Astrophysics Data System (ADS)

    Miyahara, Takashi; Oizumi, Masanobu; Nakatani, Tatsuyuki; Sato, Takehiko

    2014-04-01

    Use of plasma in water for water treatment and medical treatment is growing and raises expectations of finding advanced functions such as an increase of biological compatibility. In the present study with a focus on the variation of oxidation-reduction potential (ORP), relationships between the electrode polarities of plasma in water and the change of water quality such as conductivity, H2O2 concentration, dissolved hydrogen concentration, pH and ORP were revealed. Similar line spectra of radiation at the electrode tip were observed for each case of positive and negative electrode polarity. The emission intensities of OH (309 nm), Hα (656 nm), and OI (777 nm) for the positive discharge were significantly higher than those for the negative one, though the energy consumption during the discharge period of both cases was nearly the same. Positive electrode polarity was found to be more suitable than negative electrode polarity for increasing dissolved hydrogen gas and hydrogen peroxide. The ORP for the positive polarity decreased from 460 to 45 mV and that for the negative polarity decreased from 460 to 183 mV, although the pH and conductivity were not significantly changed.

  14. Sulfide oxidation and nitrate reduction for potential mitigation of H2S in landfills.

    PubMed

    Fang, Yuan; Du, Yao; Feng, Huan; Hu, Li-Fang; Shen, Dong-Sheng; Long, Yu-Yang

    2015-04-01

    Because H2S emitted by landfill sites has seriously endangered human health, its removal is urgent. H2S removal by use of an autotrophic denitrification landfill biocover has been reported. In this process, nitrate-reducing and sulfide-oxidizing bacteria use a reduced sulfur source as electron donor when reducing nitrate to nitrogen gas and oxidizing sulfur compounds to sulfate. The research presented here was performed to investigate the possibility of endogenous mitigation of H2S by autotrophic denitrification of landfill waste. The sulfide oxidation bioprocess accompanied by nitrate reduction was observed in batch tests inoculated with mineralized refuse from a landfill site. Repeated supply of nitrate resulted in rapid oxidation of the sulfide, indicating that, to a substantial extent, the bioprocess may be driven by functional microbes. This bioprocess can be realized under conditions suitable for the autotrophic metabolic process, because the process occurred without addition of acetate. H2S emissions from landfill sites would be substantially reduced if this bioprocess was introduced. PMID:25680916

  15. Soil Oxidation-Reduction Potential and Plant Photosynthetic Capacity in the Northern Pantanal of Mato Grosso, Brazil

    NASA Astrophysics Data System (ADS)

    Lathuilliere, M. J.; Johnson, M. S.; Dalmagro, H. J.; Pinto Junior, O. B.; Couto, E. G.

    2013-12-01

    Plant communities of the Pantanal wetland are able to survive long periods of climatic and physiological stress in the dry and wet seasons. During inundation, soil oxygen demand increases dramatically as reducing soil conditions create stress in the root system with possible impacts on photosynthetic capacity of plants. We look at inundation cycles of a tree island (locally known as a cordilheira) in the Northern Pantanal near Poconé, Mato Grosso, and relate soil oxidation-reduction potential and soil oxygen depletion to the photosynthetic capacity of two plant communities of flooded scrub forest (Vochysia divergens and Curatela americana). Results show a drop in soil oxidation-reduction potential of over 400 mV, to levels below the absolute value of -200 mV, following inundation around the tree island. Both plant species showed increased carbon assimilation at highest soil oxygen demand despite a change in stomatal conductance, suggesting adaptation to the inundated environment. Absolute values of soil oxidation-reduction potential also allow for the determination of specific soil chemical reactions characteristic of the tree island environment, namely the reduction of iron(III), or carbon dioxide which in turn produces methane. Our combined analysis of soil chemistry with plant ecophysiology allows for a better understanding of soil-plant interactions in the Pantanal, specifically the drivers of biogeochemical processes between inundation periods.

  16. Anaerobic methane oxidation coupled to nitrite reduction can be a potential methane sink in coastal environments.

    PubMed

    Shen, Li-Dong; Hu, Bao-Lan; Liu, Shuai; Chai, Xiao-Ping; He, Zhan-Fei; Ren, Hong-Xing; Liu, Yan; Geng, Sha; Wang, Wei; Tang, Jing-Liang; Wang, Yi-Ming; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping

    2016-08-01

    In the current study, we investigated nitrite-dependent anaerobic methane oxidation (N-DAMO) as a potential methane sink in the Hangzhou Bay and the adjacent Zhoushan sea area. The potential activity of the N-DAMO process was primarily observed in Hangzhou Bay by means of (13)C-labeling experiments, whereas very low or no potential N-DAMO activity could be detected in the Zhoushan sea area. The measured potential N-DAMO rates ranged from 0.2 to 1.3 nmol (13)CO2 g(-1) (dry sediment) day(-1), and the N-DAMO potentially contributed 2.0-9.4 % to the total microbial methane oxidation in the examined sediments. This indicated that the N-DAMO process may be an alternative pathway in the coastal methane cycle. Phylogenetic analyses confirmed the presence of Candidatus Methylomirabilis oxyfera-like bacteria in all the examined sediments, while the group A members (the dominant bacteria responsible for N-DAMO) were found mainly in Hangzhou Bay. Quantitative PCR showed that the 16S rRNA gene abundance of Candidatus M. oxyfera-like bacteria varied from 5.4 × 10(6) to 5.0 × 10(7) copies g(-1) (dry sediment), with a higher abundance observed in Hangzhou Bay. In addition, the overlying water NO3 (-) concentration and salinity were identified as the most important factors influencing the abundance and potential activity of Candidatus M. oxyfera-like bacteria in the examined sediments. This study showed the evidence of N-DAMO in coastal environments and indicated the importance of N-DAMO as a potential methane sink in coastal environments. PMID:27225473

  17. GAMMA RADIATION INTERACTS WITH MELANIN TO ALTER ITS OXIDATION-REDUCTION POTENTIAL AND RESULTS IN ELECTRIC CURRENT PRODUCTION

    SciTech Connect

    Turick, C.; Ekechukwu, A.; Milliken, C.

    2011-05-17

    The presence of melanin pigments in organisms is implicated in radioprotection and in some cases, enhanced growth in the presence of high levels of ionizing radiation. An understanding of this phenomenon will be useful in the design of radioprotective materials. However, the protective mechanism of microbial melanin in ionizing radiation fields has not yet been elucidated. Here we demonstrate through the electrochemical techniques of chronoamperometry, chronopotentiometry and cyclic voltammetry that microbial melanin is continuously oxidized in the presence of gamma radiation. Our findings establish that ionizing radiation interacts with melanin to alter its oxidation-reduction potential. Sustained oxidation resulted in electric current production and was most pronounced in the presence of a reductant, which extended the redox cycling capacity of melanin. This work is the first to establish that gamma radiation alters the oxidation-reduction behavior of melanin, resulting in electric current production. The significance of the work is that it provides the first step in understanding the initial interactions between melanin and ionizing radiation taking place and offers some insight for production of biomimetic radioprotective materials.

  18. Gamma radiation interacts with melanin to alter its oxidation-reduction potential and results in electric current production.

    PubMed

    Turick, Charles E; Ekechukwu, Amy A; Milliken, Charles E; Casadevall, Arturo; Dadachova, Ekaterina

    2011-08-01

    The presence of melanin pigments in organisms is implicated in radioprotection and in some cases, enhanced growth in the presence of high levels of ionizing radiation. An understanding of this phenomenon will be useful in the design of radioprotective materials. However, the protective mechanism of microbial melanin in ionizing radiation fields has not yet been elucidated. Here we demonstrate through the electrochemical techniques of chronoamperometry, chronopotentiometry and cyclic voltammetry that microbial melanin is continuously oxidized in the presence of gamma radiation. Our findings establish that ionizing radiation interacts with melanin to alter its oxidation-reduction potential. Sustained oxidation resulted in electric current production and was most pronounced in the presence of a reductant, which extended the redox cycling capacity of melanin. This work is the first to establish that gamma radiation alters the oxidation-reduction behavior of melanin, resulting in electric current production. The significance of the work is that it provides the first step in understanding the initial interactions between melanin and ionizing radiation taking place and offers some insight for production of biomimetic radioprotective materials. PMID:21632287

  19. Measurement of the oxidation-reduction potentials for two-electron and four-electron reduction of lipoamide dehydrogenase from pig heart.

    PubMed

    Matthews, R G; Williams, C H

    1976-07-10

    The oxidation-reduction potential, E2, for the couple oxidized lipoamide dehydrogenase/2-electron reduced lipoamide dehydrogenase has been determined by measurement of equilibria of these enzyme species with lipoamide and dihydrolipoamide or with oxidized and reduced azine dyes. E2 is -0.280 V at pH 7, and deltaE2/deltapH is -0.06 V in the pH range 5.5 to 7.6. Values for E1, the oxidation-reduction potential for the couple 2-electron reduced enzyme/4-electron reduced enzyme, were obtained from measurements of the extent of dismutation of 2-electron reduced enzyme to form mixtures containing oxidized and 4-electron reduced enzyme. E1 is -0.346 V at pH 7, and deltaE1/deltapH is -0.06 V in the pH range 5.7 to 7.6. Spectra of oxidized enzyme and 4-electron reduced enzyme do not show variations with pH over this range, but the spectrum of the 2-electron reduced enzyme is pH-dependent, with the molar extinction at 530 nm changing from 3250 M-1 cm-1 at pH 8 to 2050 M-1 cm-1 at pH 5.2. The pH-dependent changes which are observed in the absorption properties of the 2-electron reduced enzyme are consistent with the disappearance of a charge transfer complex between an amino acid side chain and the oxidized flavin at the lower pH values, with the apparent pK of the side chain at pH 5. It has been suggested that the 530 nm absorbance of 2-electron reduced enzyme is due to a charge transfer complex between thiolate anion and oxidized flavin, and we propose that the thiolate anion is stabilized by interaction with a protonated base. The thermodynamic data predict that the amount of 4-electron reduced enzyme formed when the enzyme is reduced by excess NADH will be pH-dependent, with the greatest amounts seen at low pH values. These data support earlier evidence (Matthews, R.G., Wilkinson, K.D., Ballou, D,P., and Williams, C.H., Jr. (1976) in Flavins and Flavoproteins (Singer, T.P., ed) pp. 464-472; Elsevier Scientific Publishing Co., Amsterdam) that the role of NAD+ in the NADH

  20. Effects of sulfide and low redox potential on the inhibition of nitrous oxide reduction by acetylene in Pseudomonas nautica.

    PubMed

    Jensen, K M; Cox, R P

    1992-09-01

    Membrane introduction mass spectrometry was used to investigate the inhibitory effect of acetylene on the nitrous oxide reductase activity of intact cells of Pseudomonas nautica. We studied the effects of the concentrations of nitrate and sulfide, and the redox potential, which have all been implicated in causing a decrease in the inhibitory effects of acetylene during measurements of denitrification in natural environments. There was no evidence that the concentration of nitrate influenced the effect of acetylene. Lowering the redox potential with the reductant Ti(III)-nitrilotriacetate caused a slight alleviation of acetylene inhibition. Much greater effects at the same redox potential were obtained with concentrations of sulfide in the range 1-10 microM. PMID:1526461

  1. Effects of oxidation reduction potential in the bypass micro-aerobic sludge zone on sludge reduction for a modified oxic-settling-anaerobic process.

    PubMed

    Li, Kexun; Wang, Yi; Zhang, Zhongpin; Liu, Dongfang

    2014-01-01

    Batch experiments were conducted to determine the effect of oxidation reduction potential (ORP) on sludge reduction in a bypass micro-aerobic sludge reduction system. The system was composed of a modified oxic-settling-anaerobic process with a sludge holding tank in the sludge recycle loop. The ORPs in the micro-aerobic tanks were set at approximately +350, -90, -150, -200 and -250 mV, by varying the length of aeration time for the tanks. The results show that lower ORP result in greater sludge volume reduction, and the sludge production was reduced by 60% at the lowest ORP. In addition, low ORP caused extracellular polymer substances dissociation and slightly reduced sludge activity. Comparing the sludge backflow characteristics of the micro-aerobic tank's ORP controlled at -250 mV with that of +350 mV, the average soluble chemical oxygen (SCOD), TN and TP increased by 7, 0.4 and 2 times, median particle diameter decreased by 8.5 μm and the specific oxygen uptake rate (SOUR) decreased by 0.0043 milligram O2 per gram suspended solids per minute. For the effluent, SCOD and TN and TP fluctuated around 30, 8.7 and 0.66 mg/L, respectively. Therefore, the effective assignment of ORP in the micro-aerobic tank can remarkably reduce sludge volume and does not affect final effluent quality. PMID:24845332

  2. Electrolytic oxide reduction system

    SciTech Connect

    Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L; Berger, John F

    2015-04-28

    An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies, a plurality of cathode assemblies, and a lift system configured to engage the anode and cathode assemblies. The cathode assemblies may be alternately arranged with the anode assemblies such that each cathode assembly is flanked by two anode assemblies. The lift system may be configured to selectively engage the anode and cathode assemblies so as to allow the simultaneous lifting of any combination of the anode and cathode assemblies (whether adjacent or non-adjacent).

  3. Influence of the sewage sludge stabilization process on the value of its oxidation-reduction potential.

    PubMed

    Bartkowska, Izabela

    2014-01-01

    The paper presents the study of a sewage sludge subjected to the process of the autothermal thermophilic stabilization (autothermal thermophilic aerobic digestion (ATAD)), which occurs in a two-stage installation. This study was conducted at the municipal wastewater treatment installation in 2010 and 2011. A thickened sludge was examined in an intermediate tank from which it was next being transferred to successive ATAD installation reactors. The content of the dry mass and organic substances was checked in a raw sludge after the first installation stage and after the ATAD process. Also, the levels of the chemical oxygen demand, the pH and the temperature were measured. During the process, the redox potential was measured. Collected results were subjected to statistical analysis. Our main attention was focused on measurements of the redox potential and further the usefulness of this measurement for the evaluation of the process was considered. The way its values were changing was determined. In the thickened sludge prior to the ATAD process, the value of the redox potential oscillated from 329.90 mV to -108.50 mV. In the first-stage reactor, this value dropped significantly and held within a range between -509.80 mV and -214.60 mV. In the second installation stage, this value ranged between -561.60 mV and -306.40 mV. During the study, fully sanitized and stabilized sludge was obtained. The paper presents the evaluation of the conducted research and conclusions ensuing from it. PMID:25145168

  4. The influence of oxidation reduction potential and water treatment processes on quartz lamp sleeve fouling in ultraviolet disinfection reactors.

    PubMed

    Wait, Isaac W; Johnston, Cliff T; Blatchley, Ernest R

    2007-06-01

    Ultraviolet (UV) disinfection systems are incorporated into drinking water production facilities because of their broad-spectrum antimicrobial capabilities, and the minimal disinfection by-product formation that generally accompanies their use. Selection of an optimal location for a UV system within a drinking water treatment facility depends on many factors; a potentially important consideration is the effect of system location on operation and maintenance issues, including the potential for fouling of quartz surfaces. To examine the effect of system location on fouling, experiments were conducted at a groundwater treatment facility, wherein aeration, chlorination, and sand filtration were applied sequentially for treatment. In this facility, access to the water stream was available prior to and following each of the treatment steps. Therefore, it was possible to examine the effects of each of these unit operations on fouling dynamics within a UV system. Results indicated zero-order formation kinetics for the fouling reactions at all locations. Increases in oxidation reduction potential, caused by water treatment steps such as aeration and chlorination, increased the rate of sleeve fouling and the rate of irradiance loss within the reactor. Analysis of metals in the sleeve foulant showed that calcium and iron predominate, and relative comparisons of foulant composition to water chemistry highlighted a high affinity for incorporation into the foulant matrix for both iron and manganese, particularly after oxidizing treatment steps. Fouling behavior was observed to be in qualitative agreement with representations of the degree of saturation, relative to the metal:ligand combinations that are believed to comprise a large fraction of the foulants that accumulate on the surfaces of quartz jackets in UV systems used to treat water. PMID:17448518

  5. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis.

    PubMed

    Gerken, James B; Stahl, Shannon S

    2015-08-26

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NO x ) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NO x species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NO x species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NO x species, together with kinetically efficient reduction of oxidized NO x species by TEMPO and other organic nitroxyls. PMID:27162977

  6. Oxidation-reduction potentials and ionization states of extracellular peroxidases from the lignin-degrading fungus Phanerochaete chrysosporium.

    PubMed

    Millis, C D; Cai, D Y; Stankovich, M T; Tien, M

    1989-10-17

    The oxidation-reduction potentials of lignin peroxidase isozymes H1, H2, H8, and H10 as well as the Mn-dependent peroxidase isozymes H3 and H4 are reported. The potentiometric titrations involving the ferrous and ferric states of the enzyme had Nernst plots indicating single-electron transfer. The Em7 values of lignin peroxidase isozymes H1, H2, H8, and H10 are -142, -135, -137, and -127 mV versus standard hydrogen electrode, respectively. The Em7 values for the Mn-dependent peroxidase isozymes H3 and H4 are -88 and -93 mV versus standard hydrogen electrode, respectively. The midpoint potential of H1, H8, and H4 remained unchanged in the presence of their respective substrates, veratryl alcohol and Mn(II). The midpoint potential between the ferric and ferrous forms of isozymes H1 and H4 exhibited a pH-dependent change between pH 3.5 and pH 6.5. These results indicate that the reductive half-reaction of the enzymes is the following: ferric peroxidase + le- + H+----ferrous peroxidase. Above pH 6.5, the effect of pH on the midpoint potential is diminished and indicates that an ionization with an apparent pKa equal to approximately 6.6-6.7 occurs in the reduced form of the enzymes. A heme-linked ionization group in the ferrous form of the enzymes was confirmed by studying the effect of pH on the absorption spectra of isozymes H1 and H4. These spectrophotometric pH titration experiments confirmed the electrochemical results indicating pKa values of 6.59 and 6.69 for reduced isozymes H1 and H4, respectively. These results indicate the presence of a heme-linked ionization of an amino acid in the reduced form of the lignin peroxidase isozymes similar to that of other plant peroxidases. PMID:2605198

  7. Characteristics of oxidation-reduction potential, VFAs, SCOD, N, and P in an ATAD system under different thermophilic temperatures.

    PubMed

    Cheng, Jiehong; Kong, Feng; Zhu, Jun; Wu, Xiao

    2015-01-01

    One-stage autoheated thermophilic aerobic digestion (ATAD) can stabilize sludge to meet class A standard. In this study, batch experiments were conducted to investigate the characteristics of oxidation-reduction potential (ORP), volatile fatty acids (VFAs), soluble chemical oxygen demand (SCOD), and nutrients at different temperatures (45, 55, and 65 °C) in the one-stage ATAD. Results showed that the ORP values remained between approximately -350 and -120 mV in the primary 5-day digestion despite of excessive aeration in the digester, indicating that the aeration level could be decreased in an ATAD system to save energy. The pH exhibited a poor correlation (R (2) < 0.11) with ORP, indicating that some variables synthetically effected on pH. Digestion at 65 °C caused more intercellular compounds released because of the highest concentrations of SCOD, VFA, nitrogen (N) and phosphorus (P) in the solution among three digestion temperatures. The volatile suspended solid (VSS) removal rate for sludge at 55 °C was the highest among three digestion temperatures, reaching 41.4 % on day 13 and meeting Class A standard. VSS removal rate of 30.1 % under 65 °C did not satisfy the effluent standard because of the high soluble content of ammonium nitrogen. The majority of nitrogen and phosphorus left in the sludge supernatant under 65 °C could hinder its further use for land applications. Therefore, the optimal temperature of 55 °C is suitable for the ATAD process. PMID:25245680

  8. Direct electrochemical reduction of metal-oxides

    DOEpatents

    Redey, Laszlo I.; Gourishankar, Karthick

    2003-01-01

    A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

  9. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend.

    PubMed

    Godoi, Ricardo H M; Polezer, Gabriela; Borillo, Guilherme C; Brown, Andrew; Valebona, Fabio B; Silva, Thiago O B; Ingberman, Aline B G; Nalin, Marcelo; Yamamoto, Carlos I; Potgieter-Vermaak, Sanja; Penteado Neto, Renato A; de Marchi, Mary Rosa R; Saldiva, Paulo H N; Pauliquevis, Theotonio; Godoi, Ana Flavia L

    2016-08-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP(ESR)) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP(ESR) results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100cm(-1) and 1600cm(-1) indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. PMID:27101453

  10. Electro-catalytic reduction of nitrogen oxides

    SciTech Connect

    McLarnon, C.R.

    1989-12-01

    Nitrogen oxides have been linked to a broad range of air pollution problems including acid rain and the atmospheric production of photochemical ozone. Over twenty million tons of nitrogen oxides are emitted into the atmosphere each year as a result of the high temperature combustion of fossil fuels. Efforts to control nitrogen oxides emissions have lagged because of the generally low discharge concentrations of nitrogen oxides in combustion exhaust and because nitrogen oxides are more difficult to remove due to their lower reactivity. No catalyst has yet been found that will achieve significant reduction of nitrogen oxides in an oxidizing environment. Oxygen in the exhaust stream competes with nitrogen oxides for the active catalyst sites. Also, the dissociated oxygen atoms produced by decomposition of nitrogen oxides deactivate the surface of the catalyst. Externally applied electric fields have been used to control oxygen adsorption on metal and semi-conductor surfaces. In this investigation, a stream containing nitric oxide has been subjected to intense electric fields in the presence of catalyst materials including steel, stainless steel, and gold plated stainless steel wools and glass wool. The electric fields have been generated using DC, AC and rectified AC potentials in the range of 0--20 KV. The effect of parameters such as inlet nitric oxide concentration, oxygen and water content, gas residence time and temperature have also been studied.

  11. Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria

    PubMed Central

    Klueglein, Nicole; Zeitvogel, Fabian; Stierhof, York-Dieter; Floetenmeyer, Matthias; Konhauser, Kurt O.; Obst, Martin

    2014-01-01

    Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers (Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ∼8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record. PMID:24271182

  12. Destruction of TCE Using Oxidative and Reductive Pathways as Potential In-Situ Treatments for the Contaminated Paducah Groundwater

    SciTech Connect

    Lewis, S; Li, Y; Xu, J; Tee, Y; Lynch, Andrew

    2007-05-01

    When considering reductive technologies for ground water remediation, it is important to understand the underlying principles that govern kinetics of zero-valent metal dechlorination. Studies involving the use of nanoscale metals (characteristic length <100nm) for chloro-organic degradation have increased reaction rates by 1-2 orders of magnitude with minimal intermediate formation. Typically, these metals are synthesized using modifications of the aqueous phase reduction of metal ions using sodium borohydride presented by Glavee and coworkers. The use of a bimetallic system increases the reactivity of the particle surface by incorporating a second metal that can typically act as a hydrogenation promotor.

  13. Potential benefits of physical activity during pregnancy for the reduction of gestational diabetes prevalence and oxidative stress.

    PubMed

    Cid, Marcela; González, Marcelo

    2016-03-01

    Changes in quality of nutrition, habits, and physical activity in modern societies increase susceptibility to obesity, which can deleteriously affect pregnancy outcome. In particular, a sedentary lifestyle causes dysfunction in blood flow, which impacts the cardiovascular function of pregnant women. The main molecular mechanism responsible for this effect is the synthesis and bioavailability of nitric oxide, a phenomenon regulated by the antioxidant capacity of endothelial cells. These alterations affect the vascular health of the mother and vascular performance of the placenta, the key organ responsible for the healthy development of the fetus. In addition to the increases in systemic vascular resistance in the mother, placental oxidative stress also affects the feto-placental blood flow. These changes can be integrated into the proteomics and metabolomics of newborns. PMID:26833143

  14. Benzene oxidation coupled to sulfate reduction

    USGS Publications Warehouse

    Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

    1995-01-01

    Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

  15. Intrinsic anion oxidation potentials.

    PubMed

    Johansson, Patrik

    2006-11-01

    Anions of lithium battery salts have been investigated by electronic structure calculations with the objective to find a computational measure to correlate with the observed (in)stability of nonaqueous lithium battery electrolytes vs oxidation often encountered in practice. Accurate prediction of intrinsic anion oxidation potentials is here made possible by computing the vertical free energy difference between anion and neutral radical (Delta Gv) and further strengthened by an empirical correction using only the anion volume as a parameter. The 6-311+G(2df,p) basis set, the VSXC functional, and the C-PCM SCRF algorithm were used. The Delta Gv calculations can be performed using any standard computational chemistry software. PMID:17078600

  16. Nitrous oxide reduction genetic potential from the microbial community of an intermittently aerated partial nitritation SBR treating mature landfill leachate.

    PubMed

    Gabarró, J; Hernández-Del Amo, E; Gich, F; Ruscalleda, M; Balaguer, M D; Colprim, J

    2013-12-01

    This study investigates the microbial community dynamics in an intermittently aerated partial nitritation (PN) SBR treating landfill leachate, with emphasis to the nosZ encoding gene. PN was successfully achieved and high effluent stability and suitability for a later anammox reactor was ensured. Anoxic feedings allowed denitrifying activity in the reactor. The influent composition influenced the mixed liquor suspended solids concentration leading to variations of specific operational rates. The bacterial community was low diverse due to the stringent conditions in the reactor, and was mostly enriched by members of Betaproteobacteria and Bacteroidetes as determined by 16S rRNA sequencing from excised DGGE melting types. The qPCR analysis for nitrogen cycle-related enzymes (amoA, nirS, nirK and nosZ) demonstrated high amoA enrichment but being nirS the most relatively abundant gene. nosZ was also enriched from the seed sludge. Linear correlation was found mostly between nirS and the organic specific rates. Finally, Bacteroidetes sequenced in this study by 16S rRNA DGGE were not sequenced for nosZ DGGE, indicating that not all denitrifiers deal with complete denitrification. However, nosZ encoding gene bacteria was found during the whole experiment indicating the genetic potential to reduce N2O. PMID:24183561

  17. Molecular Modeling of Environmentally Important Processes: Reduction Potentials

    ERIC Educational Resources Information Center

    Lewis, Anne; Bumpus, John A.; Truhlar, Donald G.; Cramer, Christopher J.

    2004-01-01

    The increasing use of computational quantum chemistry in the modeling of environmentally important processes is described. The employment of computational quantum mechanics for the prediction of oxidation-reduction potential for solutes in an aqueous medium is discussed.

  18. INFLUENCE OF PH AND OXIDATION-REDUCTION POTENTIAL (EH) ON THE DISSOLUTION OF MERCURY-CONTAINING MINE WASTES FROM THE SULFUR BANK MERCURY MINE

    EPA Science Inventory

    This study was undertaken as a part of developing treatment alternatives for waste materials, primarily waste rock and roaster tailings, from sites contaminated with mercury (Hg) mining wastes. Leaching profiles of waste rock over a range of different pH and oxidation-reduction (...

  19. Oxidation and Reduction Reactions in Organic Chemistry

    ERIC Educational Resources Information Center

    Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

    2010-01-01

    A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

  20. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  1. Missing aerobic-phase nitrogen: The potential for heterotrophic reduction of autotrophically generated nitrous oxide in a sequencing batch reactor wastewater treatment system.

    PubMed

    Shiskowskii, D M; Mavinic, D S

    2005-08-01

    Several biochemical pathways can induce nitrogen loss from aerated, aerobic wastewater treatment bioreactors. These pathways include "traditional" simultaneous nitrification-denitrification (SND) (i.e. autotrophic nitrification - heterotrophic denitrification), autotrophic denitrification, and anaerobic ammonia oxidation. An oxygen limitation, often expressed in terms of low dissolved oxygen (DO) concentration, is a common element of these pathways. The presented research investigated the effect of mixed liquor DO concentration and biomass slowly degradable carbon (SDC) utilization rate on the heterotrophic nitrous oxide (N2O) reduction rate, for biomass cultured in an anoxic/aerobic wastewater treatment bioreactor. Biomass oxygen and SDC availability-limitation, expressed in terms of DO concentration and SDC ultilization rate, respectively, were found to significantly impact the observed heterotrophic N2O reduction rate. The findings support the hypothesis that nitrogen lost from the mixed liquor of an aerobic bioreactor could result from simultaneous autotrophic N2O generation (i.e. autotrophic denitrification) and heterotrophic N2O reduction. The results also support the idea that autotrophic N2O generation could be occurring in a bioreactor, although N2O may not be measurable in the reactor off-gas. Therefore, this autotrophic N2O generation - heterotrophic N2O reduction mechanism provides an alternative explanation to nitrogen loss, when compared to "conventional" SND, where heterotrophic organisms are assumed to reduce autotrophically generated nitrite and nitrate to dinitrogen (N2). In addition, nitrogen loss speculatively attributed to N2 formation via anaerobic ammonia oxidation in oxygen-limited environments, again because of the absence of measurable N2O, may in fact be due to the autotrophic N2O generation - heterotrophic N2O reduction mechanism. PMID:16128383

  2. The variations of Oxidation-Reduction Potential in paddy soil and effects on the methane emission from a periodically irrigated paddy field.

    NASA Astrophysics Data System (ADS)

    Yagi, K.; Iwata, T.; Wakikuromaru, N.

    2014-12-01

    Paddy fields are one of the most important eco-system in monsoon Asia and one of the largest source of CH4 emission. CH4 has significant contribution to the global warming next to CO2 and its greenhouse effect is about 21 times as large as same amount of CO2. CH4 is generated by decomposition of organic matter in soil under anaerobic condition. Oxidation-Reduction Potential (ORP) is the most suitable index representing soil aerobic condition. Or, CH4 is more generated under lower ORP conditions. In this study, ORP in paddy soil was measured during rice cultivated season at a periodically irrigated paddy field, and some effects on the methane flux from the paddy soil was investigated. 3-days flood and 4-days drained condition were regularly repeated at the site from late-June to early October. ORP under flooded condition was measured during irrigated term in 2013 at two mode; regular interval measurement every 2 weeks and intensive measurements during two flooded periods. Methane flux was also measured by the aerodynamic gradient technique. ORP showed rapid decrease when irrigation water was introduced in the paddy field, and lower ORP was shown under the longer flooded condition. From the seasonal-term point of view, lower ORP was shown in later rice season. ORP was suitably modeled as a function of irrigation time. During an irrigation period for four days, higher methane emissions were shown under lower OPR conditions as shown in Fig.1. From the seasonal-term point of view, however, no significant relationship between ORP and methane fluxes. Rapid rise of CH4 flux in early August and gradual decrease between late August and September were shown. It is suggested that seasonal change of methane flux is affected by seasonal changes of soil temperature or the growth level of rice plants.

  3. Reduction of metal oxides through mechanochemical processing

    DOEpatents

    Froes, Francis H.; Eranezhuth, Baburaj G.; Senkov, Oleg N.

    2000-01-01

    The low temperature reduction of a metal oxide using mechanochemical processing techniques. The reduction reactions are induced mechanically by milling the reactants. In one embodiment of the invention, titanium oxide TiO.sub.2 is milled with CaH.sub.2 to produce TiH.sub.2. Low temperature heat treating, in the range of 400.degree. C. to 700.degree. C., can be used to remove the hydrogen in the titanium hydride.

  4. High-Resolution Distribution of Temperature, Particle and Oxidation/Reduction Potential Anomalies From a Submarine Hydrothermal System: Brothers Volcano, Kermadec Arc

    NASA Astrophysics Data System (ADS)

    Walker, S. L.; Baker, E. T.; de Ronde, C. E.; Yoerger, D.; Embley, R. W.; Davy, B.; Merle, S. G.; Resing, J. A.; Nakamura, K.

    2008-12-01

    The complex relationships between geological setting and hydrothermal venting have, to date, largely been explored with ship-based surveys that effectively examine regional relationships, or with remotely operated vehicles (ROV) and manned submersibles which allow close examination of individual vent fields. Higher- resolution surveys than are possible with ship-based techniques and broader surveys than are practical with ROVs and manned submersibles are necessary for more thoroughly understanding hydrothermal systems and their impact on ocean ecosystems. Autonomous vehicles (AUVs), such as the WHOI Autonomous Benthic Explorer (ABE) can be programmed to conduct high-resolution surveys that systematically cover a broad area of seafloor. Brothers volcano, a hydrothermally active submarine caldera volcano located on the Kermadec arc northwest of New Zealand, was surveyed in July-August 2007 using ABE. Brothers caldera is ~3 km in diameter with a floor depth of 1850 m and walls that rise 290-530 m above the caldera floor. A dacite cone with a summit depth of ~1200 m sits within the caldera, partially merging with the southern caldera wall. Prior to the survey, active hydrothermal vents were known to be perched along the NW caldera wall and located at three sites on the cone. The enclosed caldera, presence of known vent fields with differing geochemical characteristics, and existence of at least one currently inactive site made Brothers volcano an ideal site for a high-resolution survey to explore in greater detail the mass, thermal and geochemical exchanges of hydrothermal systems. During our expedition, the caldera walls and dacite cone (~7 km2) were completely surveyed by ABE with 50-60 m trackline spacing at an altitude of 50 m above the seafloor. Hydrothermal plumes were mapped with ABE's integrated CTD (conductivity- temperature-depth) and sensors measuring optical backscatter (particle concentrations) and oxidation- reduction potential (ORP; indicating the

  5. Stabilized tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2008-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  6. Extracellular Dopamine Potentiates Mn-Induced Oxidative Stress, Lifespan Reduction, and Dopaminergic Neurodegeneration in a BLI-3–Dependent Manner in Caenorhabditis elegans

    PubMed Central

    Benedetto, Alexandre; Au, Catherine; Avila, Daiana Silva; Milatovic, Dejan; Aschner, Michael

    2010-01-01

    Parkinson's disease (PD)-mimicking drugs and pesticides, and more recently PD-associated gene mutations, have been studied in cell cultures and mammalian models to decipher the molecular basis of PD. Thus far, a dozen of genes have been identified that are responsible for inherited PD. However they only account for about 8% of PD cases, most of the cases likely involving environmental contributions. Environmental manganese (Mn) exposure represents an established risk factor for PD occurrence, and both PD and Mn-intoxicated patients display a characteristic extrapyramidal syndrome primarily involving dopaminergic (DAergic) neurodegeneration with shared common molecular mechanisms. To better understand the specificity of DAergic neurodegeneration, we studied Mn toxicity in vivo in Caenorhabditis elegans. Combining genetics and biochemical assays, we established that extracellular, and not intracellular, dopamine (DA) is responsible for Mn-induced DAergic neurodegeneration and that this process (1) requires functional DA-reuptake transporter (DAT-1) and (2) is associated with oxidative stress and lifespan reduction. Overexpression of the anti-oxidant transcription factor, SKN-1, affords protection against Mn toxicity, while the DA-dependency of Mn toxicity requires the NADPH dual-oxidase BLI-3. These results suggest that in vivo BLI-3 activity promotes the conversion of extracellular DA into toxic reactive species, which, in turn, can be taken up by DAT-1 in DAergic neurons, thus leading to oxidative stress and cell degeneration. PMID:20865164

  7. Size dependent reduction-oxidation-reduction behaviour of cobalt oxide nanocrystals.

    PubMed

    Sadasivan, Sajanikumari; Bellabarba, Ronan M; Tooze, Robert P

    2013-11-21

    Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal particles led to solid spheres, hollow spheres or core-shell structures depending on the size of the initial metal particle. Further re-reduction of the oxidized structures was also observed to be size dependent. The hollow oxide shells formed by the large particles (29 nm) fragmented into smaller particles on reduction, while the hollow shells of the medium sized particles (11 nm) did not re-disperse on further reduction. Similarly, no re-dispersion was observed in the case of the small particles (6 nm). This model study provides useful insights into the size dependent behavior of metal/metal oxide particles during oxidation/reduction. This has important implications in petrochemical industry where cobalt is used as a catalyst in the Fischer-Tropsch process. PMID:24065040

  8. Graphene oxide reduction by microwave heating

    NASA Astrophysics Data System (ADS)

    Longo, Angela; Carotenuto, Gianfranco

    2016-05-01

    The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

  9. Reduction of Metal Oxide to Metal using Ionic Liquids

    SciTech Connect

    Dr. Ramana Reddy

    2012-04-12

    A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode

  10. Oxidation-reduction capacities of aquifer solids

    SciTech Connect

    Barcelona, M.J.; Holm, T.R.

    1991-01-01

    Oxidation-reduction processes play a major role in the mobility, transport, and fate of inorganic and organic chemical constituents in natural waters. Therefore, the manipulation of redox conditions in natural and treated water systems is assumed to be a common option for the control of contaminant concentrations. Measurements of the oxidation (i.e., of aqueous Cr(2+)) and reduction (i.e., of aqueous Cr2O7(2-) and H2O2) capacities of aquifer solids and groundwater have been made on samples from a sand-and-gravel aquifer. The groundwater contributed less than 1% of the system oxidation or reduction poising capacity. Reduction capacities averaged 0.095, 0.111, and 0.136 mequiv/g of dry solids for oxic, transitional, and reducing Eh conditions, respectively. Measured oxidation capacities averaged 0.4 mequiv/g of dry solids over the range of redox intensity conditions. These capacities represent considerable resistance to the adjustment of redox conditions even at uncontaminated sites. Hydrogen peroxide reduction by aquifer solid samples proceeds rapidly relative to microbially mediated decomposition. The study indicates the need for closer scrutiny of the predictability and cost effectiveness of attempts to manipulate redox conditions in poorly poised aquifer systems.

  11. Size dependent reduction-oxidation-reduction behaviour of cobalt oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Sadasivan, Sajanikumari; Bellabarba, Ronan M.; Tooze, Robert P.

    2013-10-01

    Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal particles led to solid spheres, hollow spheres or core-shell structures depending on the size of the initial metal particle. Further re-reduction of the oxidized structures was also observed to be size dependent. The hollow oxide shells formed by the large particles (29 nm) fragmented into smaller particles on reduction, while the hollow shells of the medium sized particles (11 nm) did not re-disperse on further reduction. Similarly, no re-dispersion was observed in the case of the small particles (6 nm). This model study provides useful insights into the size dependent behavior of metal/metal oxide particles during oxidation/reduction. This has important implications in petrochemical industry where cobalt is used as a catalyst in the Fischer-Tropsch process.Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal

  12. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    SciTech Connect

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  13. OXIDATION-REDUCTION CAPACITIES OF AQUIFER SOLIDS

    EPA Science Inventory

    Measurements of the oxidation (i.e., of aqueous Cr2+) and reduction (i.e., of aqueous Cr2O72- and H202) capacities of aquifer solids and groundwater have been made on samples from a sand-and-gravel aquifer. The gro...

  14. 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.

  15. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    SciTech Connect

    Grimes, Travis Shane; Mincher, Bruce Jay; Schmitt, Nicholas C

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  16. Some Tungsten Oxidation-Reduction Chemistry: A Paint Pot Titration.

    ERIC Educational Resources Information Center

    Pickering, Miles; Monts, David L.

    1982-01-01

    Reports an oxidation-reduction experiment using tungsten, somewhat analogous to the classical student experiment involving oxidation-reduction of vanadium. Includes experimental procedures, results, and toxicity/cost of tungsten compounds. (Author/JN)

  17. Oxidation-reduction catalyst and its process of use

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

    2008-01-01

    This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

  18. Lithium metal reduction of plutonium oxide to produce plutonium metal

    DOEpatents

    Coops, Melvin S.

    1992-01-01

    A method is described for the chemical reduction of plutonium oxides to plutonium metal by the use of pure lithium metal. Lithium metal is used to reduce plutonium oxide to alpha plutonium metal (alpha-Pu). The lithium oxide by-product is reclaimed by sublimation and converted to the chloride salt, and after electrolysis, is removed as lithium metal. Zinc may be used as a solvent metal to improve thermodynamics of the reduction reaction at lower temperatures. Lithium metal reduction enables plutonium oxide reduction without the production of huge quantities of CaO--CaCl.sub.2 residues normally produced in conventional direct oxide reduction processes.

  19. Analysis of potential helicopter vibration reduction concepts

    NASA Technical Reports Server (NTRS)

    Landgrebe, A. J.; Davis, M. W.

    1985-01-01

    Results of analytical investigations to develop, understand, and evaluate potential helicopter vibration reduction concepts are presented in the following areas: identification of the fundamental sources of vibratory loads, blade design for low vibration, application of design optimization techniques, active higher harmonic control, blade appended aeromechanical devices, and the prediction of vibratory airloads. Primary sources of vibration are identified for a selected four-bladed articulated rotor operating in high speed level flight. The application of analytical design procedures and optimization techniques are shown to have the potential for establishing reduced vibration blade designs through variations in blade mass and stiffness distributions, and chordwise center-of-gravity location.

  20. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy. PMID:26633757

  1. Extraction radiopolarography for determining the oxidation potentials of transplutonium elements

    SciTech Connect

    Kosyakov, V.N.; Yakovlev, N.G.; Vlasov, M.M.

    1987-03-01

    A method is described for determining the oxidation potentials for valency transitions in transplutonium elements (TPE), which is usable when the element is present in trace amounts. This is based on electrochemical oxidation or reduction of the TPE in combination with a solvent-extraction method of determining the concentration ratio for the oxidized and reduced forms. The method is applicable to determining the potential of almost any reversible reaction if the solvent-extraction parameters for the oxidized and reduced forms differ substantially, while the potential (with allowance for the extraction system) lies in a region accessible to electrochemical oxidation or reduction. Two forms of use are considered: with liquid extraction and with extraction chromatography. The method is demonstrated on the Bk(IV)/Bk(III) transition with di-2-ethylhexylphosphoric acid as extraction agent.

  2. Catalyst for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  3. Graphite Oxide: Structure, Reduction and Applications

    NASA Astrophysics Data System (ADS)

    Gao, Wei

    This thesis proposes a modified structure model for graphite oxide (GO), an important precursor in graphene chemistry, develops a new strategy to convert GO back to graphene-like structure, and demonstrates its possible applications in both water purification and supercapacitor technologies. GO, a nontraditional compound first obtained from graphite oxidation over 150 years ago, is now becoming an important player in the production of graphene-based materials, which has high technological relevance. GO structure and reduction have been vigorously investigated, but its precise chemical structure still remains obscure, and the complete restoration of the sp2 carbon lattice has not yet been achieved. In our work, solid state 13C NMR (MAS) analysis offered a piece of evidence for five or six-membered ring lactol structure existing in GO that had never been assigned before, leading to a modified Lerf-Klinowski model for GO. A three-step reduction strategy, involving sodium borohydride (NaBH4), sulfuric acid, and high temperature thermal annealing, described in the thesis, successfully reduced GO back to chemically converted graphene (CCG) with the lowest heteroatom abundance among all those previously reported. In addition to the chemical significance of graphene/CCG production, GO and its derivatives were used as novel adsorbents in water purification. GO-coated sand showed higher retention than ordinary sand for both Rhodamine B and mercuric ion (Hg2+) contaminants in water. Further functionalization of GO with thiophenol resulted in better adsorption capacity toward Hg2+ than that of activated carbon. In addition, free-standing films of GO were treated and reduced with a CO 2 laser beam into different conductive reduced GO (RGO) patterns, and directly used as supercapacitor devices which showed good cyclic stability and energy storage capacities comparable to that of existing thin film ultracapacitors. GO turned out to be a solid electrolyte with anisotropic proton

  4. Potential reduction of DSN uplink energy cost

    NASA Technical Reports Server (NTRS)

    Dolinsky, S.; Degroot, N. F.

    1982-01-01

    DSN Earth stations typically transmit more power than that required to meet minimum specifications for uplink performance. Energy and cost savings that could result from matching the uplink power to the amount required for specified performance are studied. The Galileo mission was selected as a case study. Although substantial reduction in transmitted energy is possible, potential savings in source energy (oil or electricity) savings are much less. This is because of the rising inefficiency in power conversion and radio frequency power generation that accompanies reduced power output.

  5. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  6. Treatment of oxide spent fuel using the lithium reduction process

    SciTech Connect

    Karell, E.J.; Pierce, R.D.; Mulcahey, T.P.

    1996-05-01

    The wide variety in the composition of DOE spent nuclear fuel complicates its long-term disposition because of the potential requirement to individually qualify each type of fuel for repository disposal. Argonne National Laboratory (ANL) has developed the electrometallurgical treatment technique to convert all of these spent fuel types into a single set of disposal forms, simplifying the qualification process. While metallic fuels can be directly processed using the electrometallurgical treatment technique, oxide fuels must first be reduced to the metallic form. The lithium reduction process accomplishes this pretreatment. In the lithium process the oxide components of the fuel are reduced using lithium at 650 C in the presence of molten LiCl, yielding the corresponding metals and Li{sub 2}O. The reduced metal components are then separated from the LiCl salt phase and become the feed material for electrometallurgical treatment. A demonstration test of the lithium reduction process was successfully conducted using a 10-kg batch of simulated oxide spent fuel and engineering-scale equipment specifically constructed for that purpose. This paper describes the lithium process, the equipment used in the demonstration test, and the results of the demonstration test.

  7. Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

    SciTech Connect

    Yongxin Zhao; Michael D. Mann; Edwin S. Olson; John H. Pavlish; Grant E. Dunham

    2006-05-15

    This paper is particularly related to elemental mercury (Hg{sup 0}) oxidation and divalent mercury (Hg{sup 2+} reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO{sub 2}). As a powerful oxidant and chlorinating reagent, Cl{sub 2} has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO{sub 2}, NO, as well as H{sub 2}O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO{sub 2} and NO on Hg{sup 0} oxidation and Hg{sup 2+} reduction with the intent of unraveling unrecognized interactions among Cl species, SO{sub 2}, and NO most importantly in the presence of H{sub 2}O. The experimental results demonstrated that SO{sub 2} and NO had pronounced inhibitory effects on Hg{sup 0} oxidation at high temperatures when H{sub 2}O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg{sup 2+} back into its elemental form. Data revealed that SO{sub 2} and NO were capable of promoting homogeneous reduction of Hg{sup 2+} to Hg{sup 0} with H{sub 2}O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H{sub 2}O was removed from the gas blend. 23 refs., 8 figs.

  8. Oxidation-Reduction Resistance of Advanced Copper Alloys

    NASA Technical Reports Server (NTRS)

    Greenbauer-Seng, L. (Technical Monitor); Thomas-Ogbuji, L.; Humphrey, D. L.; Setlock, J. A.

    2003-01-01

    Resistance to oxidation and blanching is a key issue for advanced copper alloys under development for NASA's next generation of reusable launch vehicles. Candidate alloys, including dispersion-strengthened Cu-Cr-Nb, solution-strengthened Cu-Ag-Zr, and ODS Cu-Al2O3, are being evaluated for oxidation resistance by static TGA exposures in low-p(O2) and cyclic oxidation in air, and by cyclic oxidation-reduction exposures (using air for oxidation and CO/CO2 or H2/Ar for reduction) to simulate expected service environments. The test protocol and results are presented.

  9. SERS speciation of the electrochemical oxidation-reduction of riboflavin.

    PubMed

    Bailey, Matthew R; Schultz, Zachary D

    2016-08-15

    The reduction and oxidation of the flavin system is an important electron transfer reaction in biological systems. Several reaction pathways exist to connect oxidized to fully reduced riboflavin, each with unique intermediates including a semi-quinone radical. By performing surface-enhanced Raman scattering (SERS) with simultaneous electrochemical detection of riboflavin at different pH values, we are able to correlate reversible changes in spectral features to the current changes observed in the cyclic voltammetry. Multivariate curve resolution analysis of the SERS spectra indicates that three distinct components were present at the SERS electrode at each pH during the potential sweep. To verify and better understand the variations in Raman bands across the voltammogram, density functional theory (DFT) calculations were performed to model the effect of pH and oxidation state on the riboflavin Raman spectrum. The calculated spectra show qualitative agreement with the species identified in the chemometric analysis. This combination of results indicates the presence of the oxidized, semi-quinone, and reduced forms of riboflavin and provides insight into the mechanism of the flavin redox system. PMID:27297697

  10. Incipient hydrous oxide species as inhibitors of reduction processes at noble metal electrode

    SciTech Connect

    Burke, L.D.; O'Sullivan, J.F.; O'Dwyer, K.J.; Scannell, R.A.; Ahern, M.J.G.; McCarthy, M.M. )

    1990-08-01

    Evidence is presented to illustrate the important role of hydrous oxide in noble metal electrocatalysis. It was demonstrated, for instance, that in the case of gold in acid the onset/termination potential, under potential sweep conditions, for hydrazine oxidation and persulfate or iodate reduction occurred at the end of the hydrous oxide reduction peak (recorded for a thick film growth grown by potential multicycling); there was also a maximum in the faradaic ac response for gold in acid in the same region. Both gold and platinum were investigated in acid and base electrolytes. In some cases a range of potential, rather than a discrete value, was found to be involved, different species react with (or are inhibited by) different types (or coverages) of these submonolayer species. In some, possibly electrocatalytically nondemanding, reduction reactions the hydrous oxide seemed to have little effect.

  11. High potential for iron reduction in upland soils.

    PubMed

    Yang, Wendy H; Liptzin, Daniel

    2015-07-01

    Changes in the redox state of iron (Fe) can be coupled to the biogeochemical cycling of carbon (C), nitrogen, and phosphorus, and thus regulate soil C, ecosystem nutrient availability, and greenhouse gas production. However, its importance broadly in non-flooded upland terrestrial ecosystems is unknown. We measured Fe reduction in soil samples from an annual grassland, a drained peatland, and a humid tropical forest We incubated soil slurries in an anoxic glovebox for 5.5 days and added sodium acetate daily at rates up to 0.4 mg C x (g soil)(-1) x d(-1). Soil moisture, poorly crystalline Fe oxide concentrations, and Fe(II) concentrations differed among study sites in the following order: annual grassland < drained peatland < tropical forest (P < 0.001 for all characteristics). All of the soil samples demonstrated high Fe reduction potential with maximum rates over the course of the incubation averaging 1706 ± 66, 2016 ± 12, and 2973 ± 115 μg Fe x (g soil)(-1) x d(-1) (mean ± SE) for the tropical forest, annual grassland, and drained peatland, respectively. Our results suggest that upland soils from diverse ecosystems have the potential to exhibit high short-term rates of Fe reduction that may play an important role in driving soil biogeochemical processes during periods of anaerobiosis. PMID:26378323

  12. Nitrosative stress in Escherichia coli: reduction of nitric oxide.

    PubMed

    Vine, Claire E; Cole, Jeffrey A

    2011-01-01

    The ability of enteric bacteria to protect themselves against reactive nitrogen species generated by their own metabolism, or as part of the innate immune response, is critical to their survival. One important defence mechanism is their ability to reduce NO (nitric oxide) to harmless products. The highest rates of NO reduction by Escherichia coli K-12 were detected after anaerobic growth in the presence of nitrate. Four proteins have been implicated as catalysts of NO reduction: the cytoplasmic sirohaem-containing nitrite reductase, NirB; the periplasmic cytochrome c nitrite reductase, NrfA; the flavorubredoxin NorV and its associated oxidoreductase, NorW; and the flavohaemoglobin, Hmp. Single mutants defective in any one of these proteins and even the mutant defective in all four proteins reduced NO at the same rate as the parent. Clearly, therefore, there are mechanisms of NO reduction by enteric bacteria that remain to be characterized. Far from being minor pathways, the currently unknown pathways are adequate to sustain almost optimal rates of NO reduction, and hence potentially provide significant protection against nitrosative stress. PMID:21265775

  13. Oxidation and Reduction: Too Many Definitions?

    ERIC Educational Resources Information Center

    Silverstein, Todd P.

    2011-01-01

    IUPAC gives several different definitions of oxidation: loss of electrons, increase in oxidation state, loss of hydrogen, or gain of oxygen. Most introductory or general chemistry textbooks use all of these definitions at one time or another, which can lead to some confusion in the minds of first-year chemistry students. Some paradoxical…

  14. Three-Electrode Metal Oxide Reduction Cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2005-06-28

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  15. Three-electrode metal oxide reduction cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2008-08-12

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  16. DEVELOPMENT OF ELECTROCHEMICAL REDUCTION TECHNOLOGY FOR SPENT OXIDE FUELS

    SciTech Connect

    Hur, Jin-Mok; Seo, Chung-Seok; Kim, Ik-Soo; Hong, Sun-Seok; Kang, Dae-Seung; Park, Seong-Won

    2003-02-27

    The Advanced Spent Fuel Conditioning Process (ACP) has been under development at Korea Atomic Energy Research Institute (KAERI) since 1997. The concept is to convert spent oxide fuel into metallic form and to remove high heat-load fission products such as Cs and Sr from the spent fuel. The heat power, volume, and radioactivity of spent fuel can decrease by a factor of a quarter via this process. For the realization of ACP, a concept of electrochemical reduction of spent oxide fuel in Li2O-LiCl molten salt was proposed and several cold tests using fresh uranium oxides have been carried out. In this new electrochemical reduction process, electrolysis of Li2O and reduction of uranium oxide are taking place simultaneously at the cathode part of electrolysis cell. The conversion of uranium oxide to uranium metal can reach more than 99% ensuring the feasibility of this process.

  17. [Competitive Microbial Oxidation and Reduction of Arsenic].

    PubMed

    Yang, Ting-ting; Bai, Yao-hui; Liang, Jin-song; Huo, Yang; Wang, Ming-xing; Yuan, Lin-ijang

    2016-02-15

    Filters are widely applied in drinking water treatment plants. Our previous study, which explored the asenic redox in a filter of drinking water plant treating underground water, found that As3+ could be oxidized to As5+ by biogenic manganese oxides, while As5+ could be reduced to As3+ by some microbial arsenic reductases in the biofilter system. This microbial competition could influence the system stability and treatment efficiency. To explore its mechanism, this study selected a manganese-oxidizing bacterial strain (Pseudomonas sp. QJX-1) and a arsenic-reducing strain (Brevibacterium sp. LSJ-9) to investigate their competitive relationship in nutrient acquisition and arsenic redox in the presence of Mn2+, As3+ or As5+ The results revealed that the concentration and valence of Mn and As varied with different reaction time; biological manganese oxides dominated the arsenic redox by rapidly oxidizing the As3+ in the existing system and the As3+ generated by arsenic reductase into As. PCR and RT-PCR results indicated that the arsenic reductase (arsC) was inhibited by the manganese oxidase (cumA). The expression of 16S rRNA in QJX-1 was two orders of magnitude higher than that in LSJ-9, which implied QJX-1 was dominant in the bacterial growth. Our data revealed that hydraulic retention time was critical to the valence of arsenic in the effluent of filter in drinking water treatment plant. PMID:27363151

  18. Oxidative reduction of glove box wipers with a downdraft thermal oxidation system

    SciTech Connect

    Phelps, M.R.; Wilcox, W.A.

    1996-04-01

    Wipers (rags) used for decontamination and glove box cleanup in the Plutonium Finishing Plant often become soaked with acid and plutonium-rich solutions. After use, these wipers are rinsed in a dilute NaOH solution and dried, but the formation of unstable nitrates and the hydrogen gas caused by hydrolysis are concerns that still must be addressed. This report gives the results of testing with a small downdraft thermal oxidation system that was constructed by Pacific Northwest National Laboratory to stabilize glove wiper waste, reduce the waste volume, and reclaim plutonium. Proof-of-principle testing was conducted with eight runs using various combinations of rag moisture and chemical pretreatment. All runs went to planned completion. Results of these tests indicate that the thermal oxidation system has the potential for providing significant reductions in waste volume. Weight reductions of 150:1 were easily obtainable during this project. Modifications could result in weight reductions of over 200:1, with possible volume reductions of 500:1.

  19. Hybrid process for nitrogen oxides reduction

    SciTech Connect

    Epperly, W.R.; Sprague, B.N.

    1991-09-10

    This patent describes a process for reducing the nitrogen oxide concentration in the effluent from the combustion of a carbonaceous fuel. It comprises introducing into the effluent a first treatment agent comprising a nitrogenous composition selected from the group consisting of urea, ammonia, hexamethylenetetramine, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, NH{sub 4}-lignosulfonate, fur-furylamine, tetrahydrofurylamine, hexamethylenediamine, barbituric acid, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, biuret, 1.1{prime}-azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, calcium cyanamide, and mixtures thereof under conditions effective to reduce the nitrogen oxides concentration and ensure the presence of ammonia in the effluent; introducing into the effluent a second treatment agent comprising an oxygenated hydrocarbon at an effluent temperature of about 500{degrees} F. to about 1600{degrees} F. under conditions effective to oxidize nitric oxide in the effluent to nitrogen dioxide and ensure the presence of ammonia at a weight ratio of ammonia to nitrogen dioxide of about 1:5 to about 5:1; and contacting the effluent with an aqueous scrubbing solution having a pH of 12 or lower under conditions effective to cause nitrogen dioxide to be absorbed therein.

  20. Reductive mobilization of oxide-bound metals

    SciTech Connect

    Stone, A.T.

    1991-01-01

    We have completed a large number of experiments which examine the release of MnO{sub 2}-bound Co, Ni, and Cu. Our work has focused upon the following areas: (1) competitive adsorption among the three toxic metals and Mn(II); (2) toxic metal release upon addition of low MW organic reductants and complexants; and (3) toxic metal release upon addition of natural organic matter-rich surface waters and IHSS organic matter reference material.

  1. 41 CFR 101-30.702 - Determining item reduction potential.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 41 Public Contracts and Property Management 2 2011-07-01 2007-07-01 true Determining item... CATALOG SYSTEM 30.7-Item Reduction Program § 101-30.702 Determining item reduction potential. Item reduction studies are required where there are large numbers of generally similar items which are subject...

  2. 41 CFR 101-30.702 - Determining item reduction potential.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Determining item... CATALOG SYSTEM 30.7-Item Reduction Program § 101-30.702 Determining item reduction potential. Item reduction studies are required where there are large numbers of generally similar items which are subject...

  3. Cost-reduction potential in LMFBR design

    SciTech Connect

    Chang, Y.I.; Till, C.E.

    1983-01-01

    LWR capital costs have escalated continuously over the years to the point where today its economics represent a bar to further LWR deployment in the US. High initial costs and the promise of a similar pattern of cost escalation in succeeding years for the LMFBR would effectively stop LMFBR deployment in this country before it could even begin. LWR cost escalation in the main can be traced to large increases in both amounts and unit costs of construction materials and to greatly lengthened construction times. Innovative approaches to LMFBR design are now being pursued that show promise for substantial cost reductions particularly in those areas that have contributed most to LWR cost increases.

  4. Phyto-reduction of graphene oxide using the aqueous extract of Eichhornia crassipes (Mart.) Solms

    NASA Astrophysics Data System (ADS)

    Firdhouse, M. Jannathul; Lalitha, P.

    2014-10-01

    The aqueous extract of Eichhornia crassipes was used as reductant to produce graphene from graphene oxide by refluxing method. The complete reduction of graphene oxide was monitored using UV-Vis spectrophotometer. Characterization of graphene was made through FTIR, XRD, and Raman spectroscopy analysis. The stability of graphene was studied by thermal gravimetric analysis and zeta potential measurements. The nature and surface morphology of the synthesized graphene was analyzed by transmission electron microscopy. The production of graphene using phytoextract as reductant emphasizes on the facile method of synthesis and greener nanotechnology.

  5. ASSESSMENT OF HOUSEHOLD CARBON FOOTPRINT REDUCTION POTENTIALS

    SciTech Connect

    Kramer, Klaas Jan; Homan, Greg; Brown, Rich; Worrell, Ernst; Masanet, Eric

    2009-04-15

    The term ?household carbon footprint? refers to the total annual carbon emissions associated with household consumption of energy, goods, and services. In this project, Lawrence Berkeley National Laboratory developed a carbon footprint modeling framework that characterizes the key underlying technologies and processes that contribute to household carbon footprints in California and the United States. The approach breaks down the carbon footprint by 35 different household fuel end uses and 32 different supply chain fuel end uses. This level of end use detail allows energy and policy analysts to better understand the underlying technologies and processes contributing to the carbon footprint of California households. The modeling framework was applied to estimate the annual home energy and supply chain carbon footprints of a prototypical California household. A preliminary assessment of parameter uncertainty associated with key model input data was also conducted. To illustrate the policy-relevance of this modeling framework, a case study was conducted that analyzed the achievable carbon footprint reductions associated with the adoption of energy efficient household and supply chain technologies.

  6. Reduction Kinetics of Graphene Oxide Determined by Temperature Programmed Desorption

    NASA Astrophysics Data System (ADS)

    Ventrice, Carl; Clark, Nicholas; Field, Daniel; Geisler, Heike; Jung, Inhwa; Yang, Dongxing; Piner, Richard; Ruoff, Rodney

    2009-10-01

    Graphene oxide, which is an electrical insulator, shows promise for use in several technological applications such as dielectric layers in nanoscale electronic devices or as the active region of chemical sensors. In principle, graphene oxide films could also be used as a precursor for the formation of large-scale graphene films by either thermal or chemical reduction of the graphene oxide. In order to determine the thermal stability and reduction kinetics of graphene oxide, temperature program desorption (TPD) measurements have been performed on multilayer films of graphene oxide deposited on SiO2/Si(100) substrates. The graphene oxide was exfoliated from the graphite oxide source material by slow-stirring in aqueous solution, which produces single-layer platelets with an average lateral size of ˜10 μm. From the TPD measurements, it was determined that the decomposition process begins at ˜80 ^oC. The primary desorption products of the graphene oxide films for temperatures up to 300 ^oC are H2O, CO2, and CO, with only trace amounts of O2 being detected. An activation energy of 1.4 eV/molecule was determined by assuming an Arrhenius dependence for the decomposition process.

  7. Monothiolation and Reduction of Graphene Oxide via One-Pot Synthesis: Hybrid Catalyst for Oxygen Reduction.

    PubMed

    Chua, Chun Kiang; Pumera, Martin

    2015-04-28

    The functionalization of graphene provides diverse possibilities to improve the handling of graphene and enable further chemical transformation on graphene. Graphene functionalized with mainly heteroatom-based functional groups to enhance its chemical and physical properties is intensively pursued but often resulted in grafting of the heteroatoms as various functional groups. Here, we show that graphene oxide can be functionalized with predominantly a single type of sulfur moiety and reduced simultaneously to form monothiol-functionalized graphene. The thiol-functionalized graphene shows a high electrical conductivity and heterogeneous electron transfer rate. Graphene is also embedded with a trace amount of manganese impurities originating from a prior graphite oxidation process, which facilitates the thiol-functionalized graphene to function as a hybrid electrocatalyst for oxygen reduction reactions in alkaline medium with an onset potential lower than for Pt/C. Further characterizations of the graphene are performed with X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, and electrochemical impedance spectroscopy. This material contributes to the class of hybrids that are highly active electrocatalysts. PMID:25816194

  8. Mitomycin antibiotic reductive potential and related pharmacological activities.

    PubMed

    Pan, S S; Gonzalez, H

    1990-06-01

    Relationships of reductive potential, kinetics of enzymatic reduction, augmented oxygen consumption, and cytotoxicity were determined for seven clinically relevant mitomycin antibiotics. Potentials for one-electron reduction were obtained by cyclic voltammetry analysis in dimethyl sulfoxide with 0.1 M tetraethyl-ammonium perchlorate. These potentials were -0.55 V for N7-acetylmitomycin C, -0.61 V for mitomycin A, -0.75 V for N7-(p-hydroxyphenyl)mitomycin C, -0.79 V for N7-(dimethylamino-methylene)mitomycin C, -0.81 V for N7-(2-(4-nitrophenyldithio)-ethyl)-mitomycin C, -0.81 V for mitomycin C, and -0.89 V for porfiromycin. All seven antibiotics were reduced by xanthine oxidase and NADPH-cytochrome P450 reductase, but the rate of reduction varied for each antibiotic and each enzyme. The less negative the reductive potential of an antibiotic, the more easily that antibiotic was reduced enzymatically. These seven mitomycin antibiotics also augmented oxygen consumption by rat liver microsomes. As with their reduction by xanthine oxidase and NADPH-cytochrome P450 reductase, the less negative the reductive potential of an antibiotic, the more it augmented oxygen consumption. Cytotoxicity of each antibiotic was assessed by defining the IC50 against HCT 116 human colon carcinoma cells. A relationship between the reductive potential of these antibiotics and their cytotoxicity against HCT 116 cells was also observed. PMID:2113607

  9. A superior method for the reduction of secondary phosphine oxides.

    PubMed

    Busacca, Carl A; Lorenz, Jon C; Grinberg, Nelu; Haddad, Nizar; Hrapchak, Matt; Latli, Bachir; Lee, Heewon; Sabila, Paul; Saha, Anjan; Sarvestani, Max; Shen, Sherry; Varsolona, Richard; Wei, Xudong; Senanayake, Chris H

    2005-09-15

    [reaction: see text] Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70 degrees C. This new reduction has distinct advantages over existing technologies. PMID:16146406

  10. Potential role of punicalagin against oxidative stress induced testicular damage

    PubMed Central

    Rao, Faiza; Tian, Hui; Li, Wenqing; Hung, Helong; Sun, Fei

    2016-01-01

    Punicalagin is isolated from pomegranate and widely used for the treatment of different diseases in Chinese traditional medicine. This study aimed to evaluate the effect of Punicalagin (purity ≥98%) on oxidative stress induced testicular damage and its effect on fertility. We detected the antioxidant potential of punicalagin in lipopolysaccharide (LPS) induced oxidative stress damage in testes, also tried to uncover the boosting fertility effect of Punicalagin (PU) against oxidative stress-induced infertility. Results demonstrated that 9 mg kg−1 for 7 days treatment significantly decreases LPS induced oxidative damage in testes and nitric oxide production. The administration of oxidative stress resulted in a significant reduction in testes antioxidants GSH, T-SOD, and CAT raised LPO, but treatment with punicalagin for 7 days increased antioxidant defense GSH, T-SOD, and CAT by the end of the experiment and reduced LPO level as well. PU also significantly activates Nrf2, which is involved in regulation of antioxidant defense systems. Hence, the present research categorically elucidates the protective effect of punicalagin against LPS induced oxidative stress induced perturbation in the process of spermatogenesis and significantly increased sperm health and number. Moreover, fertility success significantly decreased in LPS-injected mice compared to controls. Mice injected with LPS had fertility indices of 12.5%, while others treated with a combination of PU + LPS exhibited 75% indices. By promoting fertility and eliminating oxidative stress and inflammation, PU may be a useful nutrient for the treatment of infertility. PMID:26763544

  11. Potential role of punicalagin against oxidative stress induced testicular damage.

    PubMed

    Rao, Faiza; Tian, Hui; Li, Wenqing; Hung, Helong; Sun, Fei

    2016-01-01

    Punicalagin is isolated from pomegranate and widely used for the treatment of different diseases in Chinese traditional medicine. This study aimed to evaluate the effect of Punicalagin (purity ≥98%) on oxidative stress induced testicular damage and its effect on fertility. We detected the antioxidant potential of punicalagin in lipopolysaccharide (LPS) induced oxidative stress damage in testes, also tried to uncover the boosting fertility effect of Punicalagin (PU) against oxidative stress-induced infertility. Results demonstrated that 9 mg kg-1 for 7 days treatment significantly decreases LPS induced oxidative damage in testes and nitric oxide production. The administration of oxidative stress resulted in a significant reduction in testes antioxidants GSH, T-SOD, and CAT raised LPO, but treatment with punicalagin for 7 days increased antioxidant defense GSH, T-SOD, and CAT by the end of the experiment and reduced LPO level as well. PU also significantly activates Nrf2, which is involved in regulation of antioxidant defense systems. Hence, the present research categorically elucidates the protective effect of punicalagin against LPS induced oxidative stress induced perturbation in the process of spermatogenesis and significantly increased sperm health and number. Moreover, fertility success significantly decreased in LPS-injected mice compared to controls. Mice injected with LPS had fertility indices of 12.5%, while others treated with a combination of PU + LPS exhibited 75% indices. By promoting fertility and eliminating oxidative stress and inflammation, PU may be a useful nutrient for the treatment of infertility. PMID:26763544

  12. Process for the reduction of nitrogen oxides in an effluent

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.; Sprague, B.N.

    1989-09-05

    This patent describes a process for the reduction of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprises introducing a heterocyclic hydrocarbon selected from the group consisting of piperazine, piperidine, pyrazine, pyrazole, imidazole, oxazolidone, pyrrole and pyrrolidine into the effluent having an effluent temperature of greater than about 1200{sup 0}F. under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

  13. Oxidation of aromatic contaminants coupled to microbial iron reduction

    USGS Publications Warehouse

    Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

    1989-01-01

    THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

  14. Hemin-functionalized reduced graphene oxide nanosheets reveal peroxynitrite reduction and isomerization activity.

    PubMed

    Vernekar, Amit A; Mugesh, Govindasamy

    2012-11-19

    Facile and efficient reduction of graphene oxide (GO) and novel applications of the reduced graphene oxide (RGO) based materials are of current interest. Herein, we report a novel and facile method for the reduction of GO by using a biocompatible reducing agent dithiothreitol (DTT). Stabilization of DTT by the formation of a six-membered ring with internal disulfide linkage upon oxidation is responsible for the reduction of GO. The reduced graphene oxide is characterized by several spectroscopic and microscopic techniques. Dispersion of RGO in DMF remained stable for several weeks suggesting that the RGO obtained by DTT-mediated reduction is hydrophobic in nature. This method can be considered for large scale production of good quality RGO. Treatment of RGO with hemin afforded a functional hemin-reduced graphene oxide (H-RGO) hybrid material that exhibited remarkable protective effects against the potentially harmful peroxynitrite (PN). A detailed inhibition study on PN-mediated oxidation and nitration reactions indicate that the interaction between hemin and RGO results in a synergistic effect, which leads to an efficient reduction of PN to nitrate. The RGO also catalyzes the isomerization of PN to nitrate as the RGO layers facilitate the rapid recombination of (·)NO(2) with Fe(IV)=O species. In the presence of reducing agents such as ascorbic acid, the Fe(IV)=O species can be reduced to Fe(III), thus helping to maintain the PN reductase cycle. PMID:23042238

  15. Effects of reduction temperature on copper nanowires growth by thermal reduction of copper oxide nanowires

    NASA Astrophysics Data System (ADS)

    Rashid, Norhana Mohamed; Kishi, Naoki; Soga, Tetsuo

    2016-06-01

    Metallic Cu nanowires have been synthesized by thermal reduction of CuO nanowires in low concentration hydrogen environment. The Cu nanowires can be formed after removing oxide group from the metal oxide nanowires within temperature range from 200∘C to 500∘C. These nanowires have twisted structure with 100-200 nm and average lengths of 10 μm can be obtained in optimum temperature range 300-400∘C reduced for 30 min. The X-ray diffraction (XRD) pattern shows Cu peaks recognized at (111), (200) and (220). Scanning electron microscopy (SEM) images reveal the reduction temperatures strongly affect the nanowires formation. Transmission electron microscopy (TEM) images confirmed that Cu nanowires have single crystalline structures with 0.21 nm fringe spacing which correspond to (111) growth direction. The results indicate that thermal reduction of copper oxide nanowires in low concentration hydrogen environment can produce high purity and single crystalline Cu nanowires.

  16. Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2011-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  17. Ion Association, Solubilities, and Reduction Potentials in Aqueous Solution.

    ERIC Educational Resources Information Center

    Russo, Steven O.; Hanania, George I. H.

    1989-01-01

    Incorporates the combined effects of ionic strength and ion association to show how calculations involving ionic equilibria are carried out. Examines the variability of reduction potential data for two aqueous redox systems. Provides several examples. (MVL)

  18. Nox control for high nitric oxide concentration flows through combustion-driven reduction

    DOEpatents

    Yeh, James T.; Ekmann, James M.; Pennline, Henry W.; Drummond, Charles J.

    1989-01-01

    An improved method for removing nitrogen oxides from concentrated waste gas streams, in which nitrogen oxides are ignited with a carbonaceous material in the presence of substoichiometric quantities of a primary oxidant, such as air. Additionally, reductants may be ignited along with the nitrogen oxides, carbonaceous material and primary oxidant to achieve greater reduction of nitrogen oxides. A scrubber and regeneration system may also be included to generate a concentrated stream of nitrogen oxides from flue gases for reduction using this method.

  19. OBSERVATIONS ON THE OXIDATION-REDUCTION PROPERTIES OF STERILE BACTERIOLOGICAL MEDIA.

    PubMed

    Dubos, R

    1929-02-28

    Sterile plain broth contains an active oxidation-reduction system, the characteristics of which have been analyzed. 1. Intensity factor: Under vaseline seal, the lot of broth used in these experiments reaches a reduction potential corresponding to reduced indigo disulfonate (rH = 10). All the indicators with a more positive E(0)' are reduced, the others are not affected. It seems probable that fresh broth, which has not undergone oxidation by molecular oxygen, would give a higher reduction potential. 2. Capacity factor: The maximum amounts of different indicators that can be reduced correspond to equimolecular concentrations. This seems to indicate either (a) that the broth does not contain several "independent" reducing systems (at least in appreciable amounts), or (b) that these hypothetical "independent" systems all have about the same reduction potential. 3. Time factor: The different indicators of oxidation-reduction potentials are reduced in the order of the electromotive series. 4. Nature of the system: The system seems to be reversible (this not excluding the possibility of irreversible autoxidations) and does not appear to be of the nature of a sugar. The relation of these phenomena to the cultivation of different species of bacteria will be reported later. PMID:19869560

  20. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes.

    PubMed

    Huang, Li-Zhi; Hansen, Hans Christian B; Bjerrum, Morten Jannik

    2016-04-01

    Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30μAcm(-2) was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400μM of the nitroaromatic compound at a potential of -0.7V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant=0.28h(-1)) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant=6.9μM h(-1)). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and low over potential. PMID:26716570

  1. Real-Time Manganese Phase Dynamics during Biological and Abiotic Manganese Oxide Reduction.

    PubMed

    Johnson, Jena E; Savalia, Pratixa; Davis, Ryan; Kocar, Benjamin D; Webb, Samuel M; Nealson, Kenneth H; Fischer, Woodward W

    2016-04-19

    Manganese oxides are often highly reactive and easily reduced, both abiotically, by a variety of inorganic chemical species, and biologically during anaerobic respiration by microbes. To evaluate the reaction mechanisms of these different reduction routes and their potential lasting products, we measured the sequence progression of microbial manganese(IV) oxide reduction mediated by chemical species (sulfide and ferrous iron) and the common metal-reducing microbe Shewanella oneidensis MR-1 under several endmember conditions, using synchrotron X-ray spectroscopic measurements complemented by X-ray diffraction and Raman spectroscopy on precipitates collected throughout the reaction. Crystalline or potentially long-lived phases produced in these experiments included manganese(II)-phosphate, manganese(II)-carbonate, and manganese(III)-oxyhydroxides. Major controls on the formation of these discrete phases were alkalinity production and solution conditions such as inorganic carbon and phosphate availability. The formation of a long-lived Mn(III) oxide appears to depend on aqueous Mn(2+) production and the relative proportion of electron donors and electron acceptors in the system. These real-time measurements identify mineralogical products during Mn(IV) oxide reduction, contribute to understanding the mechanism of various Mn(IV) oxide reduction pathways, and assist in interpreting the processes occurring actively in manganese-rich environments and recorded in the geologic record of manganese-rich strata. PMID:27018915

  2. Biological reduction of graphene oxide using plant leaf extracts.

    PubMed

    Lee, Geummi; Kim, Beom Soo

    2014-01-01

    Two-dimensional graphene has attracted significant attention due to its unique mechanical, electrical, thermal, and optical properties. Most commonly employed methods to chemically reduce graphene oxide to graphene use hydrazine or its derivatives as the reducing agent. However, they are highly hazardous and explosive. Various phytochemicals obtained from different natural sources such as leaves and peels of a plant are used as reducing agents in the preparation of different gold, silver, copper, and platinum nanoparticles. In this study, seven plant leaf extracts (Cherry, Magnolia, Platanus, Persimmon, Pine, Maple, and Ginkgo) were compared for their abilities to reduce graphene oxide. The optimized reaction conditions for the reduction of graphene oxide were determined as follows. Type of plant: Cherry (Prunus serrulata), reaction time: 12 h, composition of the reaction mixture: 16.7% v/v of plant leaf extract in total suspension, and temperature: 95°C. The degree of reduction caused by Cherry leaf extract was analyzed by elemental analysis and X-ray photoelectron spectroscopy. The reduction of graphene oxide was also confirmed by ultraviolet-visible spectroscopy, Fourier transform-infrared spectroscopy, Raman spectroscopy, X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis. PMID:24375994

  3. Effects of Manganese Oxide on Arsenic Reduction and Leaching from Contaminated Floodplain Soil.

    PubMed

    Ehlert, Katrin; Mikutta, Christian; Kretzschmar, Ruben

    2016-09-01

    Reductive release of the potentially toxic metalloid As from Fe(III) (oxyhydr)oxides has been identified as an important process leading to elevated As porewater concentrations in soils and sediments. Despite the ubiquitous presence of Mn oxides in soils and their oxidizing power toward As(III), their impact on interrelated As, Fe, and Mn speciation under microbially reducing conditions remains largely unknown. For this reason, we employed a column setup and X-ray absorption spectroscopy to investigate the influence of increasing birnessite concentrations (molar soil Fe-to-Mn ratios: 4.8, 10.2, and 24.7) on As speciation and release from an As-contaminated floodplain soil (214 mg As/kg) under anoxic conditions. Our results show that birnessite additions significantly decreased As leaching. The reduction of both As and Fe was delayed, and As(III) accumulated in birnessite-rich column parts, indicating the passivation of birnessite and its transformation products toward As(III) oxidation and the precipitation of Fe(III)(oxyhydr)oxides. Microbial Mn reduction resulted in elevated soil pH values, which in turn lowered the microbial activity in the birnessite-enriched soil. We conclude that in Mn-oxide-rich soil environments undergoing redox fluctuations, the enhanced As adsorption to newly formed Fe(III) (oxyhydr)oxides under reducing conditions leads to a transient stabilization of As. PMID:27508335

  4. Predictive tests to evaluate oxidative potential of engineered nanomaterials

    NASA Astrophysics Data System (ADS)

    Ghiazza, Mara; Carella, Emanuele; Oliaro-Bosso, Simonetta; Corazzari, Ingrid; Viola, Franca; Fenoglio, Ivana

    2013-04-01

    Oxidative stress constitutes one of the principal injury mechanisms through which particulate toxicants (asbestos, crystalline silica, hard metals) and engineered nanomaterials can induce adverse health effects. ROS may be generated indirectly by activated cells and/or directly at the surface of the material. The occurrence of these processes depends upon the type of material. Many authors have recently demonstrated that metal oxides and carbon-based nanoparticles may influence (increasing or decreasing) the generation of oxygen radicals in a cell environment. Metal oxide, such as iron oxides, crystalline silica, and titanium dioxide are able to generate free radicals via different mechanisms causing an imbalance within oxidant species. The increase of ROS species may lead to inflammatory responses and in some cases to the development of cancer. On the other hand carbon-based nanomaterials, such as fullerene, carbon nanotubes, carbon black as well as cerium dioxide are able to scavenge the free radicals generated acting as antioxidant. The high numbers of new-engineered nanomaterials, which are introduced in the market, are exponentially increasing. Therefore the definition of toxicological strategies is urgently needed. The development of acellular screening tests will make possible the reduction of the number of in vitro and in vivo tests to be performed. An integrated protocol that may be used to predict the oxidant/antioxidant potential of engineered nanoparticles will be here presented.

  5. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  6. Dissimilatory selenate reduction potentials in a diversity of sediment types

    USGS Publications Warehouse

    Steinberg, N.A.; Oremland, R.S.

    1990-01-01

    We measured potential rates of bacterial dissimilatory reduction of 75SeO42- to 75Se0 in a diversity of sediment types, with salinities ranging from freshwater (salinity = 1 g/liter) to hypersaline (salinity = 320 g/liter and with pH values ranging from 7.1 to 9.8. Significant biological selenate reduction occurred in all samples with salinities from 1 to 250 g/liter but not in samples with a salinity of 320 g/liter. Potential selenate reduction rates (25 nmol of SeO42- per ml of sediment added with isotope) ranged from 0.07 to 22 ??mol of SeO42- reduced liter-1 h-1. Activity followed Michaelis-Menten kinetics in relation to SeO42- concentration (K(m) of selenate = 7.9 to 720 ??M). There was no linear correlation between potential rates of SeO42- reduction and salinity, pH, concentrations of total Se, porosity, or organic carbon in the sediments. However, potential selenate reduction was correlated with apparent K(m) for selenate and with potential rates of denitrification (r = 0.92 and 0.81, respectively). NO3-, NO2-, MoO42-, and WO42- inhibited selenate reduction activity to different extents in sediments from both Hunter Drain and Massie Slough, Nev. Sulfate partially inhibited activity in sediment from freshwater (salinity = 1 g/liter) Massie Slough samples but not from the saline (salinity = 60 g/liter) Hunter Drain samples. We conclude that dissimilatory selenate reduction in sediments is widespread in nature. In addition, in situ selenate reduction is a first-order reaction, because the ambient concentrations of selenium oxyanions in the sediments were orders of magnitude less than their K(m)s.

  7. Dissimilatory Selenate Reduction Potentials in a Diversity of Sediment Types

    PubMed Central

    Steinberg, Nisan A.; Oremland, Ronald S.

    1990-01-01

    We measured potential rates of bacterial dissimilatory reduction of 75SeO42− to 75Se0 in a diversity of sediment types, with salinities ranging from freshwater (salinity = 1 g/liter) to hypersaline (salinity = 320 g/liter and with pH values ranging from 7.1 to 9.8. Significant biological selenate reduction occurred in all samples with salinities from 1 to 250 g/liter but not in samples with a salinity of 320 g/liter. Potential selenate reduction rates (25 nmol of SeO42− per ml of sediment added with isotope) ranged from 0.07 to 22 μmol of SeO42− reduced liter−1 h−1. Activity followed Michaelis-Menten kinetics in relation to SeO42− concentration (Km of selenate = 7.9 to 720 μM). There was no linear correlation between potential rates of SeO42− reduction and salinity, pH, concentrations of total Se, porosity, or organic carbon in the sediments. However, potential selenate reduction was correlated with apparent Km for selenate and with potential rates of denitrification (r = 0.92 and 0.81, respectively). NO3−, NO2−, MoO42−, and WO42− inhibited selenate reduction activity to different extents in sediments from both Hunter Drain and Massie Slough, Nev. Sulfate partially inhibited activity in sediment from freshwater (salinity = 1 g/liter) Massie Slough samples but not from the saline (salinity = 60 g/liter) Hunter Drain samples. We conclude that dissimilatory selenate reduction in sediments is widespread in nature. In addition, in situ selenate reduction is a first-order reaction, because the ambient concentrations of selenium oxyanions in the sediments were orders of magnitude less than their Kms. PMID:16348359

  8. Methods of Nitrogen Oxide Reduction in Pellet Boilers

    NASA Astrophysics Data System (ADS)

    Zandeckis, Aivars; Blumberga, Dagnija; Rochas, Claudio; Veidenbergs, Ivars; Silins, Kaspars

    2010-01-01

    The main goal of this research was to create and test technical solutions that reduce nitrogen oxide emissions in low-capacity pellet boiler. During the research, wood pellets were incinerated in a pellet boiler produced in Latvia with a rated capacity of 15 kW. During the research two NOx emission reduction methods were tested: secondary air supply in the chamber and recirculation of flue gases. Results indicated a drop of NOx concentration only for flue gas recirculation methods. Maximum reduction of 21% was achieved.

  9. Direct oxide reduction demonstration, small-scale studies

    SciTech Connect

    Long, J.L.; Santi, D.J.; Fisher, D.C.; Humiston, T.J.

    1991-12-09

    This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG&G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a well-defined process should minimize capital cost and maximize productivity. Reduced radiation exposure may also be realized. A detailed, statistically valid investigation of the direct oxide reduction process was carried out utilizing 100 grams or less of plutonium dioxide per experiment. Conditions were established for obtaining 95% + yields. Conclusions drawn from the results of the experimental work were utilized to make recommendations for future large-scale investigative and confirmative work as well large-scale production demonstration work. 4 refs., 5 figs., 14 tabs.

  10. Direct oxide reduction demonstration, small-scale studies

    SciTech Connect

    Long, J.L.; Santi, D.J.; Fisher, D.C.; Humiston, T.J.

    1991-12-09

    This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a well-defined process should minimize capital cost and maximize productivity. Reduced radiation exposure may also be realized. A detailed, statistically valid investigation of the direct oxide reduction process was carried out utilizing 100 grams or less of plutonium dioxide per experiment. Conditions were established for obtaining 95% + yields. Conclusions drawn from the results of the experimental work were utilized to make recommendations for future large-scale investigative and confirmative work as well large-scale production demonstration work. 4 refs., 5 figs., 14 tabs.

  11. The role of volatiles in the reduction of iron oxides

    NASA Astrophysics Data System (ADS)

    Sohn, Il

    With iron ore reduction processes using coal-ore pellets or mixtures, it is possible that volatiles from the coals can contribute to the overall reduction. By identifying the possible reducing species in the volatiles as H2/CO and simulating these constituents, the rates for H2 and CO were investigated in the temperature and reduction range of interest where hydrogen was the major reductant and studied in detail. In the initial stages of the present study, the fundamentals of hydrogen reduction of fine powder were found to be a complex mechanism of chemical kinetics and mass transfer. Complete uniform reduction for porous and dense iron ores were not observed contrary to existing work regarding this subject. Morphological observations of iron ores reduced at low and high temperatures showed a topochemical receding interface to be dominating with an intermediate region developing for higher temperature samples indicating the importance of pore mass transfer at the later stages of reduction. Although the activation energy of 50˜56 kJ/mole for these powder samples were comparable to the literature values for solely chemical kinetics controlled reactions, the reaction rates were not proportional to sample weight and also did not exhibit complete uniform internal reduction. The calculated mass transfer rates were comparable to the observed rate which suggested that bulk mass transfer is important to the mixed-control. The reaction rate at the mixed control regime was found to be first order with respect to hydrogen partial pressure. Results of reducing iron oxide powders in a mixture of He-40%H2 -5%CO and H2-1%H2S showed that H2S and CO which is involved with the volatiles does not affect the rate at the reduction range of interest indicating the role of volatiles is dominated by the hydrogen reduction. The single composite pellet experiments at 900 and 1000°C showed significant fixed carbon reduction to occur above 1000°C. Depending upon the type of carbon reductant

  12. Use of ion conductors in the pyrochemical reduction of oxides

    DOEpatents

    Miller, W.E.; Tomczuk, Z.

    1994-02-01

    An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

  13. Use of ion conductors in the pyrochemical reduction of oxides

    DOEpatents

    Miller, William E.; Tomczuk, Zygmunt

    1994-01-01

    An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

  14. Direct printing and reduction of graphite oxide for flexible supercapacitors

    SciTech Connect

    Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

    2014-08-04

    We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

  15. Reduction of iron-oxide-carbon composites: part III. Shrinkage of composite pellets during reduction

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  16. Reduction of Iron-Oxide-Carbon Composites: Part III. Shrinkage of Composite Pellets during Reduction

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  17. High Potential for Iron Reduction in Upland Soils from Diverse Terrestrial Ecosystems

    NASA Astrophysics Data System (ADS)

    Yang, W. H.; Liptzin, D.

    2014-12-01

    Changes in the redox state of iron (Fe) can be coupled to the biogeochemical cycling of carbon (C), nitrogen, and phosphorus. The importance of Fe in catalyzing redox-driven biogeochemical cycling has been underappreciated in terrestrial ecosystems because they are not typically thought of as anaerobic environments. However, upland soils can experience anaerobic conditions following rainfall events or in microsites of high biological oxygen consumption. Measurements of Fe reduction rates in soils are difficult to compare among studies from different ecosystems, so we used the same assay to quantify potential Fe reduction in soils from upland environments (annual grassland, drained peatland pasture, and a rainforest) that varied in poorly crystalline Fe and total C. We slurried the soils and incubated them in a glovebox with a dinitrogen headspace. To evaluate the role of C availability in potential Fe reduction, we added sodium acetate daily at rates up to 0.6 mg C/g soil/d. We measured methane (CH4) production, acid- extractable Fe(II), citrate-ascorbate extractable Fe oxides, and pH over 5 days to determine the timing and magnitude of Fe reduction. In relatively dry soils (< 20 % gravimetric soil moisture), Fe reduction began after one day of anaerobic incubation as slurries, but all of the soils demonstrated high Fe reduction potential. On day 3, Fe reduction rates for the 0.05 mg C/g soil/d treatment were 1535 ± 51 μg Fe(III) g-1 d-1 in the annual grassland soil, 1205 ± 42 μg Fe(III) g-1 d-1 in the drained peatland soil, and 826 ± 54 μg Fe(III) g-1 d-1 in the rainforest soil. This contrasts with the trend in poorly crystalline Fe oxide pools across the sites: 3.87 ± 0.06 μg Fe(III) g-1 in the annual grassland, 7.49 μg Fe(III) g-1 in the drained peatland, and 20.84 ± 0.19 μg Fe(III) g-1 in the rainforest soil. Across all sites, small C additions (< 0.05 mg C/g soil/day) increased Fe reduction rates while larger C additions decreased Fe reduction. Iron

  18. Potential role of bicarbonate during pyrite oxidation

    SciTech Connect

    Evangelou, V.P.; Holt, A.; Seta, A.K.

    1998-07-15

    The need to prevent the development of acid mine drainage (AMD) by oxidation of pyrite has triggered numerous investigations into the mechanisms of its oxidation. According to Frontier molecular orbital (FMO) theory, the surface-exposed sulfur atom of pyrite possesses an unshared electron pair which produces a slightly negatively charged pyrite surface that can attract cations such as Fe{sup 2+}. Because of surface electroneutrality and pH considerations, however, the pyrite surface Fe{sup 2+} coordinates OH. The authors proposed that this surface Fe{sup 2+} OH when in the presence of CO{sub 2} is converted to {minus}FeCO{sub 3} or {minus}FeHCO{sub 3}, depending on pH. In this study, using Fourier transform infrared spectroscopy (FT-IR) they demonstrated that such complexes form on the surface of pyrite and continue to persist even after a significant fraction of the surface Fe{sup 2+} was oxidized to Fe{sup 3+}. FT-IR spectra also showed the presence of two carbonyl absorption bands (1,682 and 1,653 cm{sup {minus}1}) on the surface of pyrite upon exposure to CO{sub 2} which suggested that pyrite surface carbon complexes existed in two different surface chemical environments, pointing out two potential mechanisms of pyrite surface-CO{sub 2} interactions. One potential mechanism involved formation of a pyrite surface-Fe(II)HCO{sub 3} complex, whereas a second potential mechanism involved formation of a pyrite surface-carboxylic acid group complex [{minus}Fe(II)SSCOOFe-(II)].

  19. 1. West facade of Plutonium Concentration Facility (Building 233S), ReductionOxidation ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. West facade of Plutonium Concentration Facility (Building 233-S), Reduction-Oxidation Building (REDOX-202-S) to the right. Looking east. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

  20. Nanoscale reduction of graphene oxide thin films and its characterization

    NASA Astrophysics Data System (ADS)

    Lorenzoni, M.; Giugni, A.; Di Fabrizio, E.; Pérez-Murano, Francesc; Mescola, A.; Torre, B.

    2015-07-01

    In this paper, we report on a method to reduce thin films of graphene oxide (GO) to a spatial resolution better than 100 nm over several tens of micrometers by means of an electrochemical scanning probe based lithography. In situ tip-current measurements show that an edged drop in electrical resistance characterizes the reduced areas, and that the reduction process is, to a good approximation, proportional to the applied bias between the onset voltage and the saturation thresholds. An atomic force microscope (AFM) quantifies the drop of the surface height for the reduced profile due to the loss of oxygen. Complementarily, lateral force microscopy reveals a homogeneous friction coefficient of the reduced regions that is remarkably lower than that of native graphene oxide, confirming a chemical change in the patterned region. Micro Raman spectroscopy, which provides access to insights into the chemical process, allows one to quantify the restoration and de-oxidation of the graphitic network driven by the electrochemical reduction and to determine characteristic length scales. It also confirms the homogeneity of the process over wide areas. The results shown were obtained from accurate analysis of the shift, intensity and width of Raman peaks for the main vibrational bands of GO and reduced graphene oxide (rGO) mapped over large areas. Concerning multilayered GO thin films obtained by drop-casting we have demonstrated an unprecedented lateral resolution in ambient conditions as well as an improved control, characterization and understanding of the reduction process occurring in GO randomly folded multilayers, useful for large-scale processing of graphene-based material.

  1. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L. . Kroll Inst. for Extractive Metallurgy); Averill, W.A. )

    1992-01-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  2. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L.; Averill, W.A.

    1992-05-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  3. Oxidation-Reduction Calculations in the Biochemistry Course

    ERIC Educational Resources Information Center

    Feinman, Richard D.

    2004-01-01

    Redox calculations have the potential to reinforce important concepts in bioenergetics. The intermediacy of the NAD[superscript +]/NADH couple in the oxidation of food by oxygen, for example, can be brought out by such calculations. In practice, students have great difficulty and, even when adept at the calculations, frequently do not understand…

  4. Landscape planning for agricultural nonpoint source pollution reduction III: Assessing phosphorus and sediment reduction potential

    USGS Publications Warehouse

    Diebel, M.W.; Maxted, J.T.; Robertson, D.M.; Han, S.; Vander Zanden, M. J.

    2009-01-01

    Riparian buffers have the potential to improve stream water quality in agricultural landscapes. This potential may vary in response to landscape characteristics such as soils, topography, land use, and human activities, including legacies of historical land management. We built a predictive model to estimate the sediment and phosphorus load reduction that should be achievable following the implementation of riparian buffers; then we estimated load reduction potential for a set of 1598 watersheds (average 54 km2) in Wisconsin. Our results indicate that land cover is generally the most important driver of constituent loads in Wisconsin streams, but its influence varies among pollutants and according to the scale at which it is measured. Physiographic (drainage density) variation also influenced sediment and phosphorus loads. The effect of historical land use on present-day channel erosion and variation in soil texture are the most important sources of phosphorus and sediment that riparian buffers cannot attenuate. However, in most watersheds, a large proportion (approximately 70%) of these pollutants can be eliminated from streams with buffers. Cumulative frequency distributions of load reduction potential indicate that targeting pollution reduction in the highest 10% of Wisconsin watersheds would reduce total phosphorus and sediment loads in the entire state by approximately 20%. These results support our approach of geographically targeting nonpoint source pollution reduction at multiple scales, including the watershed scale. ?? 2008 Springer Science+Business Media, LLC.

  5. Cell oxidation-reduction imbalance after modulated radiofrequency radiation.

    PubMed

    Marjanovic, Ana Marija; Pavicic, Ivan; Trosic, Ivancica

    2015-01-01

    Aim of this study was to evaluate an influence of modulated radiofrequency field (RF) of 1800 MHz, strength of 30 V/m on oxidation-reduction processes within the cell. The assigned RF field was generated within Gigahertz Transversal Electromagnetic Mode cell equipped by signal generator, modulator, and amplifier. Cell line V79, was irradiated for 10, 30, and 60 min, specific absorption rate was calculated to be 1.6 W/kg. Cell metabolic activity and viability was determined by MTT assay. In order to define total protein content, colorimetric method was used. Concentration of oxidised proteins was evaluated by enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) marked with fluorescent probe 2',7'-dichlorofluorescin diacetate were measured by means of plate reader device. In comparison with control cell samples, metabolic activity and total protein content in exposed cells did not differ significantly. Concentrations of carbonyl derivates, a product of protein oxidation, insignificantly but continuously increase with duration of exposure. In exposed samples, ROS level significantly (p < 0.05) increased after 10 min of exposure. Decrease in ROS level was observed after 30-min treatment indicating antioxidant defence mechanism activation. In conclusion, under the given laboratory conditions, modulated RF radiation might cause impairment in cell oxidation-reduction equilibrium within the growing cells. PMID:25119294

  6. Highly controllable and green reduction of graphene oxide to flexible graphene film with high strength

    SciTech Connect

    Wan, Wubo; Zhao, Zongbin; Hu, Han; Gogotsi, Yury; Qiu, Jieshan

    2013-11-15

    Graphical abstract: Highly controllable and green reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant. Self-assembly of the as-made CCG sheets results in a flexible CCG film, of which the tensile strength strongly depends on the deoxygenation degree of graphene sheets. - Highlights: • Graphene was synthesized by an effective and environmentally friendly approach. • We introduced a facile X-ray diffraction analysis method to investigate the reduction process from graphene oxide to graphene. • Flexible graphene films were prepared by self-assembly of the graphene sheets. • The strength of the graphene films depends on the reduction degree of graphene. - Abstract: Graphene film with high strength was fabricated by the assembly of graphene sheets derived from graphene oxide (GO) in an effective and environmentally friendly approach. Highly controllable reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant, in which the reduction process was monitored by XRD analysis and UV–vis absorption spectra. Self-assembly of the as-made CCG sheets results in a flexible CCG film. This method may open an avenue to the easy and scalable preparation of graphene film with high strength which has promising potentials in many fields where strong, flexible and electrically conductive films are highly demanded.

  7. Pre-converted nitric oxide gas in catalytic reduction system

    DOEpatents

    Hsiao, Mark C.; Merritt, Bernard T.; Penetrante, Bernardino M.; Vogtlin, George E.

    1999-01-01

    A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO.sub.2 in the presence of O.sub.2. The second stage serves to convert NO.sub.2 to environmentally benign gases that include N2, CO2, and H.sub.2 O. By preconverting NO to NO.sub.2 in the first stage, the efficiency of the second stage for NO.sub.x reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO.sub.2 in the presence of O.sub.2 and includes platinum/alumina, e.g., Pt/Al.sub.2 O.sub.3 catalyst. A flow of hydrocarbons (C.sub.x H.sub.y) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO.sub.2 from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO.sub.2 to N2, CO2, and H.sub.2 O, and includes a gamma-alumina .gamma.-Al.sub.2 O.sub.3. The hydrocarbons and NO.sub.x are simultaneously reduced while passing through the second catalyst.

  8. Pre-converted nitric oxide gas in catalytic reduction system

    DOEpatents

    Hsiao, M.C.; Merritt, B.T.; Penetrante, B.M.; Vogtlin, G.E.

    1999-04-06

    A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO{sub 2} in the presence of O{sub 2}. The second stage serves to convert NO{sub 2} to environmentally benign gases that include N{sub 2}, CO{sub 2}, and H{sub 2}O. By preconverting NO to NO{sub 2} in the first stage, the efficiency of the second stage for NO{sub x} reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO{sub 2} in the presence of O{sub 2} and includes platinum/alumina, e.g., Pt/Al{sub 2}O{sub 3} catalyst. A flow of hydrocarbons (C{sub x}H{sub y}) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO{sub 2} from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO{sub 2} to N{sub 2}, CO{sub 2}, and H{sub 2}O, and includes a {gamma}-Al{sub 2}O{sub 3}. The hydrocarbons and NO{sub x} are simultaneously reduced while passing through the second catalyst. 9 figs.

  9. Chemolithotrophic perchlorate reduction linked to the oxidation of elemental sulfur.

    PubMed

    Ju, Xiumin; Field, Jim A; Sierra-Alvarez, Reyes; Salazar, Margarita; Bentley, Harold; Bentley, Richard

    2007-04-15

    Perchlorate (ClO(4)(-)) contamination of ground and surface water has been recently recognized as a widespread environmental problem. Biological methods offer promising perspectives of perchlorate remediation. Facultative anaerobic bacteria couple the oxidation of organic and inorganic electron-donating substrates to the reduction of perchlorate as a terminal electron acceptor, converting it completely to the benign end-product, chloride. Insoluble inorganic substrates are of interest for low maintenance bioreactor or permeable reactive barrier systems because they can provide a long-term supply of electron donor without generating organic residuals. The main objective of this research was to investigate the feasibility of utilizing elemental sulfur (S(0)) as an insoluble electron donor for the biological reduction of perchlorate. A chemolithotrophic enrichment culture derived from aerobic activated sludge was obtained which effectively coupled the oxidation of elemental sulfur to sulfate with the reduction of perchlorate to chloride and gained energy from the process for cell growth. The enrichment culture grew at a rate of 0.41 or 0.81 1/d in the absence and presence of added organic carbon for cell growth, respectively. The enrichment culture was also shown to carry out sulfur disproportionation to a limited extent as evidenced by the formation of sulfide and sulfate in the absence of added electron acceptor. When nitrate and perchlorate were added together, the two electron acceptors were removed simultaneously after an initial partial decrease in the nitrate concentration. PMID:17009322

  10. Simultaneous Electrochemical Reduction and Delamination of Graphene Oxide Films.

    PubMed

    Wang, Xiaohan; Kholmanov, Iskandar; Chou, Harry; Ruoff, Rodney S

    2015-09-22

    Here we report an electrochemical method to simultaneously reduce and delaminate graphene oxide (G-O) thin films deposited on metal (Al and Au) substrates. During the electrochemical reaction, interface charge transfer between the G-O thin film and the electrode surface was found to be important in eliminating oxygen-containing groups, yielding highly reduced graphene oxide (rG-O). In the meantime, hydrogen bubbles were electrochemically generated at the rG-O film/electrode interface, propagating the film delamination. Unlike other metal-based G-O reduction methods, the metal used here was either not etched at all (for Au) or etched a small amount (for Al), thus making it possible to reuse the substrate and lower production costs. The delaminated rG-O film exhibits a thickness-dependent degree of reduction: greater reduction is achieved in thinner films. The thin rG-O films having an optical transmittance of 90% (λ = 550 nm) had a sheet resistance of 6390 ± 447 Ω/□ (ohms per square). rG-O-based stretchable transparent conducting films were also demonstrated. PMID:26257072

  11. Calculating Standard Reduction Potentials of [4Fe–4S] Proteins

    SciTech Connect

    Perrin, Bradley S.; Niu, Shuqiang; Ichiye, Toshiko

    2013-03-15

    The oxidation–reduction potentials of electron transfer proteins determine the driving forces for their electron transfer reactions. Although the type of redox site determines the intrinsic energy required to add or remove an electron, the electrostatic interaction energy between the redox site and its surrounding environment can greatly shift the redox potentials. Here, a method for calculating the reduction potential versus the standard hydrogen electrode, E°, of a metalloprotein using a combinatio of density functional theory and continuum electrostatics is presented. This work focuses on the methodology for the continuum electrostatics calculations, including various factors that may affect the accuracy. The calculations are demonstrated using crystal structures of six homologous HiPIPs, which give E° that are in excellent agreement with experimental results.

  12. Spectroelectrochemistry of tris(bipyridyl)silicon(IV): ligand localized reductions with potential electrochromic applications.

    PubMed

    Peloquin, Derek M; Dewitt, Domelia R; Patel, Shreya S; Merkert, Jon W; Donovan-Merkert, Bernadette T; Schmedake, Thomas A

    2015-11-21

    Tris(bipyridyl)silicon(iv) was electrochemically reduced in acetonitrile to obtain the UV-vis spectra of its reduced species. Three stable, reversible reduced states (3+, 2+, and 1+) were observed with distinct isosbestic points for each of the redox reactions. The fully oxidized state (4+) is colorless, while the reduced states were green. The absorbance spectra for the three reduced states are consistent with ligand localized reductions. Potential advantages of using these complexes in electrochromic applications are discussed. PMID:26465594

  13. Nanoscale Tunable Reduction of Graphene Oxide for Graphene Electronics

    NASA Astrophysics Data System (ADS)

    Wei, Zhongqing; Wang, Debin; Kim, Suenne; Kim, Soo-Young; Hu, Yike; Yakes, Michael K.; Laracuente, Arnaldo R.; Dai, Zhenting; Marder, Seth R.; Berger, Claire; King, William P.; de Heer, Walter A.; Sheehan, Paul E.; Riedo, Elisa

    2010-06-01

    The reduced form of graphene oxide (GO) is an attractive alternative to graphene for producing large-scale flexible conductors and for creating devices that require an electronic gap. We report on a means to tune the topographical and electrical properties of reduced GO (rGO) with nanoscopic resolution by local thermal reduction of GO with a heated atomic force microscope tip. The rGO regions are up to four orders of magnitude more conductive than pristine GO. No sign of tip wear or sample tearing was observed. Variably conductive nanoribbons with dimensions down to 12 nanometers could be produced in oxidized epitaxial graphene films in a single step that is clean, rapid, and reliable.

  14. Direct reduction processes for titanium oxide in molten salt

    NASA Astrophysics Data System (ADS)

    Suzuki, Ryosuke O.

    2007-02-01

    Molten salt electrolysis using CaCl2 is employed to produce pure titanium and its alloys directly from TiO2 and a mixture of elemental oxides, respectively, as an alternate to the Kroll process. This is because CaO, which is a reduction by-product, is highly soluble in CaCl2. Good-quality titanium containing only a small amount of residual oxygen has been successfully produced and scaled to industrial levels. Thermochemical and electrochemical bases are reviewed to optimize the process conditions. Several processes using molten salt are being examined for future progress in titanium processing.

  15. Process for the reduction of nitrogen oxides in an effluent

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.; Sprague, B.N.

    1989-07-04

    This patent describes a process for the reduction of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprises introducing a treatment agent which comprises a composition selected from the group consisting of NH/sub 4/-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose.

  16. Nanomaterial resistant microorganism mediated reduction of graphene oxide.

    PubMed

    Chouhan, Raghuraj S; Pandey, Ashish; Qureshi, Anjum; Ozguz, Volkan; Niazi, Javed H

    2016-10-01

    In this study, soil bacteria were isolated from nanomaterials (NMs) contaminated pond soil and enriched in the presence of graphene oxide (GO) in mineral medium to obtain NMs resistant bacteria. The isolated resistant bacteria were biochemically and genetically identified as Fontibacillus aquaticus. The resistant bacteria were allowed to interact with engineered GO in order to study the biotransformation in GO structure. Raman spectra of GO extracted from culture medium revealed decreased intensity ratio of ID/IG with subsequent reduction of CO which was consistent with Fourier transform infrared (FTIR) results. The structural changes and exfoliatied GO nanosheets were also evident from transmission electron microscopy (TEM) images. Ultraviolet-visible spectroscopy, high resolution X-ray diffraction (XRD) and current-voltage measurements confirmed the reduction of GO after the interaction with resistant bacteria. X-ray photoelectron spectroscopy (XPS) analysis of biotransformed GO revealed reduction of oxygen-containing species on the surface of nanosheets. Our results demonstrated that the presented method is an environment friendly, cost effective, simple and based on green approaches for the reduction of GO using NMs resistant bacteria. PMID:27248463

  17. Determination of Protein Thiol Reduction Potential by Isotope Labeling and Intact Mass Measurement.

    PubMed

    Thurlow, Sophie E; Kilgour, David P; Campopiano, Dominic J; Mackay, C Logan; Langridge-Smith, Pat R R; Clarke, David J; Campbell, Colin J

    2016-03-01

    Oxidation/reduction of thiol residues in proteins is an important type of post-translational modification that is implicated in regulating a range of biological processes. The nature of the modification makes it possible to define a quantifiable electrochemical potential (E(⊕)) for oxidation/reduction that allows cysteine-containing proteins to be ranked based on their propensity to be oxidized. Measuring oxidation of cysteine residues in proteins is difficult using standard electrochemical methods, but top-down mass spectrometry recently has been shown to enable the quantification of E(⊕) for thiol oxidations. In this paper, we demonstrate that mass spectrometry of intact proteins can be used in combination with an isotopic labeling strategy and an automated data analysis algorithm to measure E(⊕) for the thiols in both E. coli Thioredoxin 1 and human Thioredoxin 1. Our methodology relies on accurate mass measurement of proteins using liquid chromatography-mass spectroscopy (LC-MS) analyses and does not necessarily require top-down fragmentation. In addition to analyzing homogeneous protein samples, we also demonstrate that our methodology can be used to determine thiol E(⊕) measurements in samples that contain mixtures of proteins. Thus, the combination of experimential methodology and data analysis regime has the potential to make such measurements in a high-throughput manner and in a manner that is more accessible to a broad community of protein scientists. PMID:26881737

  18. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2006-04-15

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900{sup o}C to 1000{sup o}C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 degrees C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H{sub 2O generated from the reduction of Fe{sub 2}O{sub 3} by H-2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50% reduction of the iron oxide.

  19. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    NASA Astrophysics Data System (ADS)

    Sohn, I.; Fruehan, R. J.

    2006-04-01

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H2O generated from the reduction of Fe2O3 by H2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.

  20. Simultaneous reductive dissolution of iron oxide and oxidation of iodide in ice.

    NASA Astrophysics Data System (ADS)

    Kim, Kitae; Choi, Wonyong

    2015-04-01

    Iron is an important trace element controlling the metabolism and growth of all kinds of living species. Especially, the bio-availability of iron has been regarded as the limiting factor for primary productivity in HNLC (High Nutrients Low Chlorophyll) regions including Southern ocean. The dissolution of iron oxide provides enhanced the bio-availability of iron for phytoplankton growth. The halogen chemistry in polar regions is related to various important environmental processes such as Antarctic Ozone Depletion Event(ODE), mercury depletion, oxidative processes in atmosphere, and the formation of CCN (Cloud Condensation Nuclei). In this study, we investigated the reductive dissolution of iron oxide particles to produce Fe(II)aq and simultaneous oxidation of I- (iodide) to I3- (tri-iodide) in ice phase under UV irradiation or dark condition. The reductive generation of Fe(II)aq from iron oxides and oxidation of iodide to I3- were negligible in water but significantly accelerated in frozen solution both in the presence and absence of light. The enhanced reductive generation of Fe(II)aq and oxidative formation of I3- in ice were observed regardless of the various types of iron oxides [hematite (α-Fe2O3) maghemite (γ- Fe2O3), goethite (α-FeOOH), lepidocrocite (γ-FeOOH) and, magnetite (Fe3O4)]. We explained that the enhanced redox production of Fe(II)aq and I3- in ice is contributed to the freeze concentration of iodides, protons, and dissolved oxygen in the unfrozen solution. When the concentration of both iodides and protons were raised by 10-fold each, the formation of Fe(II)aq in water under UV irradiation was approached to those in ice. The outdoor experiments were carried out under ambient solar radiation in winter season of mid-latitude (Pohang, Korea: 36°N latitude) and also confirmed that the production of Fe(II)aq via reductive dissolution of iron oxide and I3- generation via I- oxidation were enhanced in frozen solution. These results suggest that iron

  1. Redox Sensitivities of Global Cellular Cysteine Residues under Reductive and Oxidative Stress.

    PubMed

    Araki, Kazutaka; Kusano, Hidewo; Sasaki, Naoyuki; Tanaka, Riko; Hatta, Tomohisa; Fukui, Kazuhiko; Natsume, Tohru

    2016-08-01

    The protein cysteine residue is one of the amino acids most susceptible to oxidative modifications, frequently caused by oxidative stress. Several applications have enabled cysteine-targeted proteomics analysis with simultaneous detection and quantitation. In this study, we employed a quantitative approach using a set of iodoacetyl-based cysteine reactive isobaric tags (iodoTMT) and evaluated the transient cellular oxidation ratio of free and reversibly modified cysteine thiols under DTT and hydrogen peroxide (H2O2) treatments. DTT treatment (1 mM for 5 min) reduced most cysteine thiols, irrespective of their cellular localizations. It also caused some unique oxidative shifts, including for peroxiredoxin 2 (PRDX2), uroporphyrinogen decarboxylase (UROD), and thioredoxin (TXN), proteins reportedly affected by cellular reactive oxygen species production. Modest H2O2 treatment (50 μM for 5 min) did not cause global oxidations but instead had apparently reductive effects. Moreover, with H2O2, significant oxidative shifts were observed only in redox active proteins, like PRDX2, peroxiredoxin 1 (PRDX1), TXN, and glyceraldehyde 3-phosphate dehydrogenase (GAPDH). Overall, our quantitative data illustrated both H2O2- and reduction-mediated cellular responses, whereby while redox homeostasis is maintained, highly reactive thiols can potentiate the specific, rapid cellular signaling to counteract acute redox stress. PMID:27350002

  2. Hemicarceplexes modify the solubility and reduction potentials of C60.

    PubMed

    Wong, Tzu-Huan; Chang, Jia-Cheng; Lai, Chien-Chen; Liu, Yi-Hung; Peng, Shie-Ming; Chiu, Sheng-Hsien

    2014-04-18

    A highly stable C60-incarcerated hemicarceplex, which retains its molecular integrity after heating at 523 K in air for at least 3 h, significantly increases the solubility of C60 in nonpolar solvents and increases the reduction potentials of the entrapped fullerene. Modification with [(η(5)-C5Me5)Ru(II)](+) dramatically increases the solubility of this hemicarceplex in polar, protic solvents (e.g., MeOH). PMID:24665822

  3. Floating Potential Probe Langmuir Probe Data Reduction Results

    NASA Technical Reports Server (NTRS)

    Morton, Thomas L.; Minow, Joseph I.

    2002-01-01

    During its first five months of operations, the Langmuir Probe on the Floating Potential Probe (FPP) obtained data on ionospheric electron densities and temperatures in the ISS orbit. In this paper, the algorithms for data reduction are presented, and comparisons are made of FPP data with ground-based ionosonde and Incoherent Scattering Radar (ISR) results. Implications for ISS operations are detailed, and the need for a permanent FPP on ISS is examined.

  4. Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

    SciTech Connect

    Deng, Baolin; Thornton, Edward C.; Cantrell, Kirk J.; Olsen, Khris B.; Amonette, James E.

    2003-06-01

    Immobilization of toxic and radioactive metals (e.g., Cr, Tc, and U) in the vadose zone by the In Situ Gaseous Reduction (ISGR) using hydrogen sulfide (H2S) is a promising technology for soil remediation. Earlier laboratory studies have shown that Cr(VI) in soil samples can be effectively immobilized by treatment with dilute gaseous H2S. A field test completed in 1999 at White Sand Missile Range, New Mexico, has shown a 70% immobilization of Cr(VI). The objective of this EMSP project is to characterize the interactions among H2S, the metal contaminants, and soil components. Understanding these interactions is needed to optimize the remediation system and to assess the long-term effectiveness of the technology. Proposed research tasks included: (A) Evaluation of the potential catalytic effect of mineral surfaces on the rate of Cr(VI) reduction by H2S and the rate of H2S oxidation by air; (B) Identification of the reactions of soil minerals with H2S and determination of associated reaction rates; (C) Evaluation of the role of soil water chemistry on the reduction of Cr(VI) by H2S; (D) Assessment of the reductive buffering capacity of H2S-reduced soil and the potential for emplacement of long-term vadose zone reactive barriers; and (E) Evaluation of the potential for immobilization of Tc and U in the vadose zone by reduction and an assessment of the potential for remobilization by subsequent reoxidation.

  5. Direct growth of flower-like manganese oxide on reduced graphene oxide towards efficient oxygen reduction reaction.

    PubMed

    Zhang, Jintao; Guo, Chunxian; Zhang, Lianying; Li, Chang Ming

    2013-07-18

    Three-dimensional manganese oxide is directly grown on reduced graphene oxide (RGO) sheets, exhibiting comparable catalytic activity, higher selectivity and better stability towards oxygen reduction reaction than those of the commercial Pt/XC-72 catalyst. PMID:23745182

  6. Low reduction potential cytochrome b5 isotypes of Giardia intestinalis.

    PubMed

    Pazdzior, Robert; Yang, Zhen Alice; Mesbahuddin, Mirfath Sultana; Yee, Janet; van der Est, Art; Rafferty, Steven

    2015-10-01

    Despite lacking mitochondria and a known pathway for heme biosynthesis the micro-aerotolerant anaerobic protozoan parasite Giardia intestinalis encodes four members of the cytochrome b5 family of electron transfer proteins, three of which are small, single-domain proteins. While these are similar in size and fold to their better-known mammalian counterparts the Giardia proteins have distinctly lower reduction potentials, ranging from -140 to -171 mV compared to +6 mV for the bovine microsomal protein. This difference is accounted for by a more polar heme environment in the Giardia proteins, as mutation of a conserved heme pocket tyrosine residue to phenylalanine in the Giardia cytochrome b5 isotype-I (gCYTb5-I Y61F) raises its reduction potential by nearly 100 mV. All three isotypes have UV-visible spectra consistent with axial coordination of the heme by a pair of histidine residues, but electron paramagnetic spectroscopy indicates that the planes of their imidazole rings are nearly perpendicular rather than coplanar as observed in mammalian cytochrome b5, which may be due to geometrical constraints imposed by a one-residue shorter spacing between the ligand pair in the Giardia proteins. Although no function has yet to be ascribed to any Giardia cytochrome b5, the presence of similar sequences in many other eukaryotes indicates that these represent an under-characterized class of low reduction potential family members. PMID:26299244

  7. Design Principles for Oxygen Reduction and Evolution on Oxide Catalysts

    NASA Astrophysics Data System (ADS)

    Shao-Horn, Yang

    2012-02-01

    Driven by growing concerns about global warming and the depletion of petroleum resources, developing renewable energy production and storage technologies represent one of the major scientific challenges of the 21^st century. A critical element in pursuit of this quest is the discovery of efficient and cost-effective catalysts used in solar fuel production via electrochemical energy conversion processes such as oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), both of which are central to the efficiencies of direct-solar and electrolytic water-splitting devices, fuel cells, and metal-air batteries. Although the Sabatier's principle provides a qualitative argument in tuning catalytic activity by varying the bond strength between catalyst surface and reactant/product (neither too strong nor too weak leading to the maximum activity at moderate bond strength), it has no predictive power to find catalysts with enhanced activity. Identifying a ``design principle'' that links catalyst properties to the catalytic activity is critical to accelerate the search for highly active catalysts based on abundant elements, and minimize the use of precious metals. Here we establish a molecular principle that governs the activities of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for oxide catalysts, where the activities primarily correlate to the σ* orbital (``eg'') occupation of surface transition-metal cations established by systematic examination of more than ten to fifteen transition-metal oxides. The intrinsic ORR and OER activities exhibit a volcano-shaped dependence on the eg occupancy and the activities peak at an eg occupancy close to unity. Our findings reflect the critical influence of the σ* orbital on the energetics of surface reaction intermediates on surface transition metal ions such as the O2^2-/OH^- displacement and the OH^- regeneration, and thus highlight the importance of surface oxide electronic structure in controlling

  8. Hydrogen Reduction of Zinc and Iron Oxides Containing Mixtures

    NASA Astrophysics Data System (ADS)

    de Siqueira, Rogério Navarro C.; de Albuquerque Brocchi, Eduardo; de Oliveira, Pamela Fernandes; Motta, Marcelo Senna

    2013-10-01

    Zinc is a metal of significant technological importance and its production from secondary sources has motivated the development of alternative processes, such as the chemical treatment of electrical arc furnace (EAF) dust. Currently, the extraction of zinc from the mentioned residue using a carbon-containing reducing agent is in the process of being established commercially and technically. In the current study, the possibility of reducing zinc from an EAF dust sample through a H2 constant flux in a horizontal oven is studied. The reduction of a synthetic oxide mixture of analogous composition is also investigated. The results indicated that the reduction process is thermodynamically viable for temperatures higher than 1123 K (850 °C), and all zinc metal produced is transferred to the gas stream, enabling its complete separation from iron. The same reaction in the presence of zinc crystals was considered for synthesizing FeZn alloys. However, for the experimental conditions employed, although ZnO reduction was indeed thermodynamically hindered because of the presence of zinc crystals (the metal's partial pressure was enhanced), the zinc metal's escape within the gaseous phase could not be effectively avoided.

  9. Efficient Direct Reduction of Graphene Oxide by Silicon Substrate

    PubMed Central

    Chan Lee, Su; Some, Surajit; Wook Kim, Sung; Jun Kim, Sun; Seo, Jungmok; Lee, Jooho; Lee, Taeyoon; Ahn, Jong-Hyun; Choi, Heon-Jin; Chan Jun, Seong

    2015-01-01

    Graphene has been studied for various applications due to its excellent properties. Graphene film fabrication from solutions of graphene oxide (GO) have attracted considerable attention because these procedures are suitable for mass production. GO, however, is an insulator, and therefore a reduction process is required to make the GO film conductive. These reduction procedures require chemical reducing agents or high temperature annealing. Herein, we report a novel direct and simple reduction procedure of GO by silicon, which is the most widely used material in the electronics industry. In this study, we also used silicon nanosheets (SiNSs) as reducing agents for GO. The reducing effect of silicon was confirmed by various characterization methods. Furthermore, the silicon wafer was also used as a reducing template to create a reduced GO (rGO) film on a silicon substrate. By this process, a pure rGO film can be formed without the impurities that normally come from chemical reducing agents. This is an easy and environmentally friendly method to prepare large scale graphene films on Si substrates. PMID:26194107

  10. Efficient Direct Reduction of Graphene Oxide by Silicon Substrate.

    PubMed

    Lee, Su Chan; Some, Surajit; Kim, Sung Wook; Kim, Sun Jun; Seo, Jungmok; Lee, Jooho; Lee, Taeyoon; Ahn, Jong-Hyun; Choi, Heon-Jin; Jun, Seong Chan

    2015-01-01

    Graphene has been studied for various applications due to its excellent properties. Graphene film fabrication from solutions of graphene oxide (GO) have attracted considerable attention because these procedures are suitable for mass production. GO, however, is an insulator, and therefore a reduction process is required to make the GO film conductive. These reduction procedures require chemical reducing agents or high temperature annealing. Herein, we report a novel direct and simple reduction procedure of GO by silicon, which is the most widely used material in the electronics industry. In this study, we also used silicon nanosheets (SiNSs) as reducing agents for GO. The reducing effect of silicon was confirmed by various characterization methods. Furthermore, the silicon wafer was also used as a reducing template to create a reduced GO (rGO) film on a silicon substrate. By this process, a pure rGO film can be formed without the impurities that normally come from chemical reducing agents. This is an easy and environmentally friendly method to prepare large scale graphene films on Si substrates. PMID:26194107

  11. Nitrous oxide emission reduction in temperate biochar-amended soils

    NASA Astrophysics Data System (ADS)

    Felber, R.; Hüppi, R.; Leifeld, J.; Neftel, A.

    2012-01-01

    Biochar, a pyrolysis product of organic residues, is an amendment for agricultural soils to improve soil fertility, sequester CO2 and reduce greenhouse gas (GHG) emissions. In highly weathered tropical soils laboratory incubations of soil-biochar mixtures revealed substantial reductions for nitrous oxide (N2O) and carbon dioxide (CO2). In contrast, evidence is scarce for temperate soils. In a three-factorial laboratory incubation experiment two different temperate agricultural soils were amended with green waste and coffee grounds biochar. N2O and CO2 emissions were measured at the beginning and end of a three month incubation. The experiments were conducted under three different conditions (no additional nutrients, glucose addition, and nitrate and glucose addition) representing different field conditions. We found mean N2O emission reductions of 60 % compared to soils without addition of biochar. The reduction depended on biochar type and soil type as well as on the age of the samples. CO2 emissions were slightly reduced, too. NO3- but not NH4+ concentrations were significantly reduced shortly after biochar incorporation. Despite the highly significant suppression of N2O emissions biochar effects should not be transferred one-to-one to field conditions but need to be tested accordingly.

  12. Electrochemical reduction of CO 2 in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Zhan, Zhongliang; Zhao, Lin

    This paper describes results on the electrochemical reduction of carbon dioxide using the same device as the typical planar nickel-YSZ cermet electrode supported solid oxide fuel cells (H 2-CO 2, Ni-YSZ|YSZ|LSCF-GDC, LSCF, air). Operation in both the fuel cell and the electrolysis mode indicates that the electrodes could work reversibly for the charge transfer processes. An electrolysis current density of ≈1 A cm -2 is observed at 800 °C and 1.3 V for an inlet mixtures of 25% H 2-75% CO 2. Mass spectra measurement suggests that the nickel-YSZ cermet electrode is highly effective for reduction of CO 2 to CO. Analysis of the gas transport in the porous electrode and the adsorption/desorption process over the nickel surface indicates that the cathodic reactions are probably dominated by the reduction of steam to hydrogen, whereas carbon monoxide is mainly produced via the reverse water gas shift reaction.

  13. Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

    DOEpatents

    Tsang, Floris Y.

    1980-01-01

    Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

  14. Promotion of Iron Oxide Reduction and Extracellular Electron Transfer in Shewanella oneidensis by DMSO

    PubMed Central

    Cheng, Yuan-Yuan; Li, Bing-Bing; Li, Dao-Bo; Chen, Jie-Jie; Li, Wen-Wei; Tong, Zhong-Hua; Wu, Chao; Yu, Han-Qing

    2013-01-01

    The dissimilatory metal reducing bacterium Shewanella oneidensis MR-1, known for its capacity of reducing iron and manganese oxides, has great environmental impacts. The iron oxides reducing process is affected by the coexistence of alternative electron acceptors in the environment, while investigation into it is limited so far. In this work, the impact of dimethyl sulphoxide (DMSO), a ubiquitous chemical in marine environment, on the reduction of hydrous ferric oxide (HFO) by S. oneidensis MR-1 was investigated. Results show that DMSO promoted HFO reduction by both wild type and ΔdmsE, but had no effect on the HFO reduction by ΔdmsB, indicating that such a promotion was dependent on the DMSO respiration. With the DMSO dosing, the levels of extracellular flavins and omcA expression were significantly increased in WT and further increased in ΔdmsE. Bioelectrochemical analysis show that DMSO also promoted the extracellular electron transfer of WT and ΔdmsE. These results demonstrate that DMSO could stimulate the HFO reduction through metabolic and genetic regulation in S. oneidensis MR-1, rather than compete for electrons with HFO. This may provide a potential respiratory pathway to enhance the microbial electron flows for environmental and engineering applications. PMID:24244312

  15. Cr(VI) reduction coupled with anaerobic oxidation of methane in a laboratory reactor.

    PubMed

    Lu, Yong-Ze; Fu, Liang; Ding, Jing; Ding, Zhao-Wei; Li, Na; Zeng, Raymond J

    2016-10-01

    The process of anaerobic oxidation of methane (AOM) is globally important because of its contribution to the carbon cycle in the environment. Besides, microorganisms play important roles in the environmental fate of chromium. However, there have been no studies to date on the interaction between methane and chromium in batch reactor systems. In this study, biological Cr(VI) reduction was investigated using methane as the sole electron donor. Isotopic (13)CH4 in the batch experiments and long-term performance in the reactor demonstrated that Cr(VI) reduction is coupled with methane oxidation. High-throughput sequencing of the 16S rRNA genes demonstrated that the microbial community had changed substantially after Cr(VI) reduction. The populations of ANME-2d archaea were enhanced, and they became the only predominant AOM-related microbe. Interestingly, other bacteria with significant increases in abundance were not reported as having the ability to reduce Cr(VI). According to these results, two mechanisms were proposed: 1) Cr(VI) is reduced by ANME-2d alone; 2) Cr(VI) is reduced by unknown Cr(VI)-reducing microbes coupled with ANME-2d. This study revealed the potential relationship between Cr(VI) reduction and CH4 oxidation, and extended our knowledge of the relationship between the AOM process and biogeochemical cycles. PMID:27395029

  16. Sulfur-reduction potential of the coals of Ohio

    SciTech Connect

    Wizzard, J.T.; Cavallaro, J.A.; Deurbrouck, A.W.

    1983-03-01

    This report presents the results of a washability study of 148 raw coal channel samples with an emphasis on sulfur reduction. These raw coals contained on the average 13.1 percent ash, 2.47 percent pyritic sulfur, 3.86 percent total sulfur, 12,585 Btu/lb, and 6.2 pounds of SO/sub 2/ emissions per million Btu, on a moisture-free basis. The complete washability data and ultimate-proximate data are presented for these samples. Each individual washability analysis is presented in Appendix A. Statistical evaluations of the washability data and ultimate-proximate analyses are presented on a coalbed basis, whenever there are six or more samples from a given coalbed. An additional evaluation is included showing the composite data interpolated at Btu recovery levels of 50, 60, 70, 80, 90, and 100 percent. Potential sulfur dioxide (SO/sub 2/) emissions are calculated for raw and clean coal fractions. These SO/sub 2/ emissions are then compared to EPA regulations governing New Stationary Sources Performance Standards. Graphical representations are given for various coal characteristics of both raw and washed coal fractions for all coalbeds with six or more samples. For coalbeds with 20 or more samples, goodness-of-fit tests were made comparing SO/sub 2/ distributions with both normal and log-normal distributions. Confidence intervals and tolerance limits are calculated and illustrated for the SO/sub 2/ emission values as a function of specific gravity for these coalbeds. In general, ash reduction, pyritic sulfur reduction, total sulfur reduction, and SO/sub 2/ emissions reduction increase as the coal is crushed to smaller top sizes and as the coal is cleaned at lower specific gravities. This report presents the reduction curves for the major coalbeds in Ohio. 39 figures, 13 tables.

  17. Transparent Conducting Oxides as Potential Thermoelectrics

    NASA Astrophysics Data System (ADS)

    Mason, Thomas

    2013-03-01

    Transparent conducting oxides (TCOs) in their less-doped semiconducting states have potential as thermoelectric oxides or TEOs. They are attractive as TEOs owing to: 1) their good thermochemical stability, 2) their n-type character (to complement existing p-type TEOs), and 3) their high electronic mobilities. The numerator of the TE figure of merit (Z), also known as the ``power factor'' (PF), is the product of the electronic conductivity and the square of the Seebeck coefficient. An experimental procedure named after its developer, ``Jonker'' analysis plots Seebeck coefficient vs. the natural logarithm of the electronic conductivity. Data for bulk ceramic specimens just prior to the onset of degeneracy tend to fall on a line of slope, k/e (k =Boltzmann constant, e =charge of the electron). From this line, the doping composition corresponding to the highest power factor can be determined and the PF optimized, based upon data from a few carefully chosen compositions. Subsequently, following a procedure originally derived by Ioffe, the zero-thermopower intercept of these Jonker lines can be directly related to the maximum achievable power factor for a given TEO. So-called ``Ioffe'' plots allow for meaningful comparisons between candidate TEO materials, and also indicate the minimum thermal conductivity required to achieve a target ZT value at the temperature of measurement. Results for TCO-based TEOs will be discussed for both simple and compound (including layered) materials. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences as part of an Energy Frontier Research Center under grant no. DE-SC0001059.

  18. Reduction in oxidatively generated DNA damage following smoking cessation

    PubMed Central

    2011-01-01

    Background Cigarette smoking is a known cause of cancer, and cancer may be in part due to effects of oxidative stress. However, whether smoking cessation reverses oxidatively induced DNA damage unclear. The current study sought to examine the extent to which three DNA lesions showed significant reductions after participants quit smoking. Methods Participants (n = 19) in this study were recruited from an ongoing 16-week smoking cessation clinical trial and provided blood samples from which leukocyte DNA was extracted and assessed for 3 DNA lesions (thymine glycol modification [d(TgpA)]; formamide breakdown of pyrimidine bases [d(TgpA)]; 8-oxo-7,8-dihydroguanine [d(Gh)]) via liquid chromatography tandem mass spectrometry (LC-MS/MS). Change in lesions over time was assessed using generalized estimating equations, controlling for gender, age, and treatment condition. Results Overall time effects for the d(TgpA) (χ2(3) = 8.068, p < 0.045), d(PfpA) (χ2(3) = 8.477, p < 0.037), and d(Gh) (χ2(3) = 37.599, p < 0.001) lesions were seen, indicating levels of each decreased significantly after CO-confirmed smoking cessation. The d(TgpA) and d(PfpA) lesions show relatively greater rebound at Week 16 compared to the d(Gh) lesion (88% of baseline for d(TgpA), 64% of baseline for d(PfpA), vs 46% of baseline for d(Gh)). Conclusions Overall, results from this analysis suggest that cigarette smoking contributes to oxidatively induced DNA damage, and that smoking cessation appears to reduce levels of specific damage markers between 30-50 percent in the short term. Future research may shed light on the broader array of oxidative damage influenced by smoking and over longer durations of abstinence, to provide further insights into mechanisms underlying carcinogenesis. PMID:21569419

  19. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  20. Facile and controllable electrochemical reduction of graphene oxide and its applications

    SciTech Connect

    Shao, Yuyan; Wang, Jun; Engelhard, Mark H.; Wang, Chong M.; Lin, Yuehe

    2010-01-01

    Graphene oxide is electrochemically reduced which is called electrochemically reduced graphene oxide (ER-G). ER-G is characterized with scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The oxygen content is significantly decreased and the sp 2 carbon is restored after electrochemical reduction. ER-G exhibits much higher electrochemical capacitance and cycling durability than carbon nanotubes (CNTs) and chemically reduced graphene; the specific capacitance measured with cyclic voltammetry (20 mV/s) is ~165 F/g, ~86 F/g, and ~100 F/g for ER-G, CNTs, and chemically reduced graphene,1 respectively. The electrochemical reduction of oxygen and hydrogen peroxide was greatly enhanced on ER-G electrodes as compared with CNTs. ER-G has shown a good potential for applications in energy storage, biosensors, and electrocatalysis.

  1. Novel graphite salts of high oxidizing potential

    SciTech Connect

    McCarron, E.M. III

    1980-08-01

    The intercalation of graphite by the third-transition-series metal hexafluorides has yielded the graphite salts, C/sub 8//sup +/OsF/sub 6//sup -/, C/sub 8//sup +/IrF/sub 6//sup -/ and C/sub 12//sup 2 +/PtF/sub 6//sup 2 -/. The fluoroplatinate salt represents the highest electron withdrawal from the graphite network yet achieved. Analogues to the Os and Ir salts have been obtained both by fluorination of Group V pentaflouride intercalates, C/sub 8/MF/sub 5/ (M = As, Sb), and by the interaction of the dioxygenyl salts with graphite (8C + O/sub 2/MF/sub 6/ ..-->.. C/sub 8/MF/sub 6/ + O/sub 2/+). Non-intercalating binary fluorides have been observed to intercalate in the presence of a fluorine-rich environment (e.g., 8C + PF/sub 5/ + 1/2 F/sub 2/ ..-->.. C/sub 8/PF/sub 6/). GeF/sub 4/, which also does not spontaneously intercalate graphite, has been observed to interact with graphite in the presence of 2 atmospheres of fluorine overpressure to give the fluoroplatinate salt analogue, C/sub 12//sup 2 +/GeF/sub 6//sup 2 -/. This material is in equilibrium with the pentafluorogermanate at ordinary pressures and temperatures. C/sub 12//sup 2 +/GeF/sub 6//sup 2 -/ ..-->.. C/sub 12//sup +/GeF/sub 5//sup -/ + 1/2 F/sub 2/. C/sub 12/GeF/sub 6/ must have an oxidizing potential close to that of fluorine itself. The graphite fluorometallate salts are both electronic and ionic (F/sup -/) conductors. For the C/sub 8//sup +/MF/sub 6//sup -/ salts, a maximum electronic conductivity an order of magnitude greater than the parent graphite has been observed for stage two. The high oxidizing potential, coupled with the fluoride ion transport capability of the graphite salts, has been exploited in the construction of solid-state galvanic cells. These cells use the graphite fluorometallate salts as electrode materials in combination with a superionic fluoride-ion-conducting solid electrolyte.

  2. Potential for Landing Gear Noise Reduction on Advanced Aircraft Configurations

    NASA Technical Reports Server (NTRS)

    Thomas, Russell H.; Nickol, Craig L.; Burley, Casey L.; Guo, Yueping

    2016-01-01

    The potential of significantly reducing aircraft landing gear noise is explored for aircraft configurations with engines installed above the wings or the fuselage. An innovative concept is studied that does not alter the main gear assembly itself but does shorten the main strut and integrates the gear in pods whose interior surfaces are treated with acoustic liner. The concept is meant to achieve maximum noise reduction so that main landing gears can be eliminated as a major source of airframe noise. By applying this concept to an aircraft configuration with 2025 entry-into-service technology levels, it is shown that compared to noise levels of current technology, the main gear noise can be reduced by 10 EPNL dB, bringing the main gear noise close to a floor established by other components such as the nose gear. The assessment of the noise reduction potential accounts for design features for the advanced aircraft configuration and includes the effects of local flow velocity in and around the pods, gear noise reflection from the airframe, and reflection and attenuation from acoustic liner treatment on pod surfaces and doors. A technical roadmap for maturing this concept is discussed, and the possible drag increase at cruise due to the addition of the pods is identified as a challenge, which needs to be quantified and minimized possibly with the combination of detailed design and application of drag reduction technologies.

  3. Reduction of Oxidative Melt Loss of Aluminum and Its Alloys

    SciTech Connect

    Dr. Subodh K. Das; Shridas Ningileri

    2006-03-17

    identified as the primary factor that accelerates dross formation specifically in the transition from two phases to three phase growth. Limiting magnesium oxidation on the surface of molten aluminum therefore becomes the key to minimizing melt loss, and technology was developed to prevent magnesium oxidation on the aluminum surface. This resulted in a lot of the work being focused on the control of Mg oxidation. Two potential molten metal covering agents that could inhibit dross formation during melting and holding consisting of boric acid and boron nitride were identified. The latter was discounted by industry as it resulted in Boron pick up by the melt beyond that allowed by specifications during plant trials. The understanding of the kinetics of dross formation by the industry partners helped them understand how temperature, alloy chemistry and furnace atmosphere (burner controls--e.g. excess air) effected dross formation. This enables them to introduce in their plant process changes that reduced unnecessary holding at high temperatures, control burner configurations, reduce door openings to avoid ingress of air and optimize charge mixes to ensure rapid melting and avoid excess oxidation.

  4. Thermogravimetric study of reduction of oxides present in oxidized nickel-base alloy powders

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.

    1976-01-01

    Carbon, hydrogen, and hydrogen plus carbon reduction of three oxidized nickel-base alloy powders (a solid solution strengthened alloy both with and without the gamma prime formers aluminum and titanium and the solid solution strengthened alloy NiCrAlY) were evaluated by thermogravimetry. Hydrogen and hydrogen plus carbon were completely effective in reducing an alloy containing chromium, columbium, tantalum, molybdenum, and tungsten. However, with aluminum and titanium present the reduction was limited to a weight loss of about 81 percent. Carbon alone was not effective in reducing any of the alloys, and none of the reducing conditions were effective for use with NiCrAlY.

  5. Direct chemical reduction of neptunium oxide to neptunium metal using calcium and calcium chloride

    NASA Astrophysics Data System (ADS)

    Squires, Leah N.; Lessing, Paul

    2016-04-01

    A process of direct reduction of neptunium oxide to neptunium metal using calcium metal as the reducing agent is discussed. After reduction of the oxide to metal, the metal is separated by density from the other components of the reaction mixture and can be easily removed upon cooling. The direct reduction technique consistently produces high purity (98%-99% pure) neptunium metal.

  6. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  7. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-08-19

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  8. Reduction of oxidized cytochrome c by ascorbate ion.

    PubMed

    Williams, N H; Yandell, J K

    1985-11-27

    The kinetics and mechanism of the reduction of oxidized cytochrome c by ascorbate has been investigated in potassium nitrate, potassium 4-morpholineethanesulfonate (KMes), potassium sulfate and potassium ascorbate media. The results are consistent with simple second order electron transfer from ascorbate dianion to cytochrome c and do not support electron transfer from an ascorbate dianion bound to the protein of the cytochrome as recently proposed by Myer and Kumar. A rate constant of 8 X 10(5) M-1 X s-1 (25 degrees C, ionic strength, 0.1) was found for the electron-transfer step. This rate constant is essentially independent of the specific ions used in controlling ionic strength. PMID:2998459

  9. Reductive Potential - A Savior Turns Stressor in Protein Aggregation Cardiomyopathy

    PubMed Central

    Narasimhan, Madhusudhanan; Rajasekaran, Namakkal S.

    2015-01-01

    Redox homeostasis is essential for basal signaling of several physiological processes, but a unilateral shift towards an ‘oxidative’ or ‘reductive’ trait will alter intracellular redox milieu. Typically, such an event influences the structure and the native function of a cell or an organelle. Numerous experimental research and clinical trials over the last 6 decades have demonstrated that enhanced oxygen-derived free radicals constitutes a major stimuli to trigger damage in several human diseases, including cardiovascular complications supporting the theory of oxidative stress (OS). However, until our key discovery, the dynamic interrelationship between “Reductive Stress (RS)” and cardiac health has been obscured by overwhelming OS studies (Rajasekaran et al., 2007). Notably, this seminal finding spurred considerable interest in investigations of other mechanistic insights, and thus far the results indicate a similar or stronger role for RS, than that of OS. In addition, from our own findings we strongly believe that constitutive activation of pathways that enable sustained generation of reducing equivalents glutathione (GSH), reduced nicotinamide adenine dinucleotide phosphate (NADPH) will cause RS and impair the basal cellular signaling mechanisms operating through harmless pro-oxidative events, in turn, disrupting single and/or a combination of key cellular processes such as growth, maturation, differentiation, survival, death etc., that govern healthy cell physiology. Here, we have discussed the role of RS as a causal or contributing factor in relevant pathophysiology of a major cardiac disease of human origin. PMID:25446995

  10. Microbial Sulfate Reduction and Its Potential Utility as an Acid Mine Water Pollution Abatement Procedure

    PubMed Central

    Tuttle, Jon H.; Dugan, Patrick R.; Randles, Chester I.

    1969-01-01

    The presence of high concentrations of sulfate, iron, and hydrogen (acid) ions in drainage from coal mines and other areas containing waste pyritic materials is a serious water pollution problem. Sulfate can be removed from solution by microbial reduction to sulfide and subsequent precipitation as FeS. A mixed culture of microorganisms degraded wood dust cellulose, and the degradation products served as carbon and energy sources for sulfate-reducing bacteria. Metabolism of carbon compounds resulted in a net pH increase in the system. Oxidation-reduction potential (Eh) and temperature and carbon supplements were studied in an effort to accelerate the sulfate reduction process, with the ultimate objective of utilizing the process as a pollution abatement procedure. PMID:5775914

  11. Nitrate Reduction Functional Genes and Nitrate Reduction Potentials Persist in Deeper Estuarine Sediments. Why?

    PubMed Central

    Papaspyrou, Sokratis; Smith, Cindy J.; Dong, Liang F.; Whitby, Corinne; Dumbrell, Alex J.; Nedwell, David B.

    2014-01-01

    Denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the sediment column. This

  12. Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

    DOE PAGESBeta

    Salter-Blanc, Alexandra; Bylaska, Eric J.; Johnston, Hayley; Tratnyek, Paul G.

    2015-02-11

    The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. The susceptibility of energetic NACs to nitro reduction might be predicted from correlations between rate constants (k) for this reaction and one-electron reduction potentials (E1NAC) / 0.059 V, but the mechanistic implications of such correlations are inconsistent with evidence from other methods. To address this inconsistency, we have reevaluated existing kinetic data using a (non-linear) free-energy relationship (FER) based on the Marcus theory of outer-sphere electron transfer. For most reductants, the results are inconsistent with rate limitation bymore » an initial, outer-sphere electron transfer, suggesting that the strong correlation between k and E1NAC is justified only as an empirical model. This empirical correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of k for non-energetic NAC reduction by Fe(II) porphyrin and newly reported values of E1NAC determined using density functional theory at the B3LYP/6-311++G(2d,2p) level with the COSMO solvation model. The QSAR was then validated for energetic NACs using newly measured kinetic data for 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to energetic NACs.« less

  13. Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

    SciTech Connect

    Salter-Blanc, Alexandra; Bylaska, Eric J.; Johnston, Hayley; Tratnyek, Paul G.

    2015-02-11

    The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. The susceptibility of energetic NACs to nitro reduction might be predicted from correlations between rate constants (k) for this reaction and one-electron reduction potentials (E1NAC) / 0.059 V, but the mechanistic implications of such correlations are inconsistent with evidence from other methods. To address this inconsistency, we have reevaluated existing kinetic data using a (non-linear) free-energy relationship (FER) based on the Marcus theory of outer-sphere electron transfer. For most reductants, the results are inconsistent with rate limitation by an initial, outer-sphere electron transfer, suggesting that the strong correlation between k and E1NAC is justified only as an empirical model. This empirical correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of k for non-energetic NAC reduction by Fe(II) porphyrin and newly reported values of E1NAC determined using density functional theory at the B3LYP/6-311++G(2d,2p) level with the COSMO solvation model. The QSAR was then validated for energetic NACs using newly measured kinetic data for 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to energetic NACs.

  14. Drag reduction in turbulent pipe flow by applied electric potentials

    NASA Astrophysics Data System (ADS)

    Waskaas, Magne; Daujotis, Vytautas; Wolden, Kjell; Raudonis, Rimantas; Plausinaitis, Deivis

    2006-11-01

    A novel approach to drag reduction is presented on the basis of applied positive electric potentials to a pipe. This has been studied by measuring the pressure drop over a 13.1 m epoxy-coated pipe made of carbon steel, through which water was flowing under conditions of constant flow rate. Potentials were applied between the pipe and the counter electrode located at the pipe inlet. The results show a decrease in the pressure drop (up to 2%) when positive electric DC-potentials in the range 0.6 -- 1.6V were applied to the pipe. However, no significant changes was obtained for applied potentials in the ranges of 0 to 0.6 V, 1.6 to 2.0 V or 0 to -2.0 V. Waterflow through an epoxy coated turbine pipe (length 1562 m, diameter 1 m, total fall 380 m) in a hydroelectric power plant has also been studied. A 1.1 V potential was applied between the pipe and the manlock (made of stainless steel and electrically insulated from the pipe). Results show that the head loss decreased from 45.9 m to 39.8 m at maximum flow rate, which corresponds to a 1.8% increase in the electricity production. Although small, the effect represents the possibility of significant cost savings. The mechanism by which the drag is reduced is not currently understood.

  15. A micro-nano porous oxide hybrid for efficient oxygen reduction in reduced-temperature solid oxide fuel cells

    PubMed Central

    Da Han; Liu, Xuejiao; Zeng, Fanrong; Qian, Jiqin; Wu, Tianzhi; Zhan, Zhongliang

    2012-01-01

    Tremendous efforts to develop high-efficiency reduced-temperature (≤ 600°C) solid oxide fuel cells are motivated by their potentials for reduced materials cost, less engineering challenge, and better performance durability. A key obstacle to such fuel cells arises from sluggish oxygen reduction reaction kinetics on the cathodes. Here we reported that an oxide hybrid, featuring a nanoporous Sm0.5Sr0.5CoO3−δ (SSC) catalyst coating bonded onto the internal surface of a high-porosity La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) backbone, exhibited superior catalytic activity for oxygen reduction reactions and thereby yielded low interfacial resistances in air, e.g., 0.021 Ω cm2 at 650°C and 0.043 Ω cm2 at 600°C. We further demonstrated that such a micro-nano porous hybrid, adopted as the cathode in a thin LSGM electrolyte fuel cell, produced impressive power densities of 2.02 W cm−2 at 650°C and 1.46 W cm−2 at 600°C when operated on humidified hydrogen fuel and air oxidant. PMID:22708057

  16. Catalytic Protein Film Electrochemistry Provides a Direct Measure of the Tetrathionate/Thiosulfate Reduction Potential.

    PubMed

    Kurth, Julia M; Dahl, Christiane; Butt, Julea N

    2015-10-21

    The tetrathionate/thiosulfate interconversion is a two-electron process: S4O6(2-) + 2 e(-) ↔ 2 S2O3(2-). Both transformations can support bacterial growth since S2O3(2-) provides an energy source, while S4O6(2-) serves as respiratory electron acceptor. Interest in the corresponding S2O3(2-) oxidation also arises from its widespread use in volumetric analysis of oxidizing agents and bleach neutralization during water treatment. Here we report protein film electrochemistry that defines the reduction potential of the S4O6(2-)/S2O3(2-) couple. The relevant interconversion is not reversible at inert electrodes. However, facile reduction of S4O6(2-) to S2O3(2-) and the reverse reaction are catalyzed by enzymes of the thiosulfate dehydrogenase, TsdA, family adsorbed on graphite electrodes. Zero-current potentials measured with different enzymes, at three pH values, and multiple S4O6(2-) and S2O3(2-) concentrations together with the relevant Nernst equation resolved the tetrathionate/thiosulfate reduction potential as +198 ± 4 mV versus SHE. This potential lies in the ∼250 mV window encompassing previously reported values calculated from parameters including the free energy of formation. However, the value is considerably more positive than widely used in discussions of bacterial bioenergetics. As a consequence anaerobic respiration by tetrathionate reduction is likely to be more prevalent than presently thought in tetrathionate-containing environments such as marine sediments and the human gut. PMID:26437022

  17. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides.

    PubMed

    Lehninger, A L; Vercesi, A; Bababunmi, E A

    1978-04-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca(2+) and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca(2+) is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as beta-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca(2+). Successive cycles of Ca(2+) release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca(2+)-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca(2+), mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. PMID:25436

  18. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

    PubMed Central

    Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

    1978-01-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca2+ and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

  19. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella Oneidensis MR-1

    PubMed Central

    Shi, Liang; Rosso, Kevin M.; Clarke, Tomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.

    2012-01-01

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC, and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to MtrA either directly or indirectly through other periplasmic proteins. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III). In addition to Fe(III) oxides, Mtr pathway is also involved in reduction of

  20. Depletion of reduction potential and key energy generation metabolic enzymes underlies tellurite toxicity in Deinococcus radiodurans.

    PubMed

    Anaganti, Narasimha; Basu, Bhakti; Gupta, Alka; Joseph, Daisy; Apte, Shree Kumar

    2015-01-01

    Oxidative stress resistant Deinococcus radiodurans surprisingly exhibited moderate sensitivity to tellurite induced oxidative stress (LD50 = 40 μM tellurite, 40 min exposure). The organism reduced 70% of 40 μM potassium tellurite within 5 h. Tellurite exposure significantly modulated cellular redox status. The level of ROS and protein carbonyl contents increased while the cellular reduction potential substantially decreased following tellurite exposure. Cellular thiols levels initially increased (within 30 min) of tellurite exposure but decreased at later time points. At proteome level, tellurite resistance proteins (TerB and TerD), tellurite reducing enzymes (pyruvate dehydrogense subunits E1 and E3), ROS detoxification enzymes (superoxide dismutase and thioredoxin reductase), and protein folding chaperones (DnaK, EF-Ts, and PPIase) displayed increased abundance in tellurite-stressed cells. However, remarkably decreased levels of key metabolic enzymes (aconitase, transketolase, 3-hydroxy acyl-CoA dehydrogenase, acyl-CoA dehydrogenase, electron transfer flavoprotein alpha, and beta) involved in carbon and energy metabolism were observed upon tellurite stress. The results demonstrate that depletion of reduction potential in intensive tellurite reduction with impaired energy metabolism lead to tellurite toxicity in D. radiodurans. PMID:25331933

  1. Effects of oxidants and reductants on the efficiency of excitation transfer in green photosynthetic bacteria

    NASA Technical Reports Server (NTRS)

    Wang, J.; Brune, D. C.; Blankenship, R. E.

    1990-01-01

    The efficiency of energy transfer in chlorosome antennas in the green sulfur bacteria Chlorobium vibrioforme and Chlorobium limicola was found to be highly sensitive to the redox potential of the suspension. Energy transfer efficiencies were measured by comparing the absorption spectrum of the bacteriochlorophyll c or d pigments in the chlorosome to the excitation spectrum for fluorescence arising from the chlorosome baseplate and membrane-bound antenna complexes. The efficiency of energy transfer approaches 100% at low redox potentials induced by addition of sodium dithionite or other strong reductants, and is lowered to 10-20% under aerobic conditions or after addition of a variety of membrane-permeable oxidizing agents. The redox effect on energy transfer is observed in whole cells, isolated membranes and purified chlorosomes, indicating that the modulation of energy transfer efficiency arises within the antenna complexes and is not directly mediated by the redox state of the reaction center. It is proposed that chlorosomes contain a component that acts as a highly quenching center in its oxidized state, but is an inefficient quencher when reduced by endogenous or exogenous reductants. This effect may be a control mechanism that prevents cellular damage resulting from reaction of oxygen with reduced low-potential electron acceptors found in the green sulfur bacteria. The redox modulation effect is not observed in the green gliding bacterium Chloroflexus aurantiacus, which contains chlorosomes but does not contain low-potential electron acceptors.

  2. Reduction potential and heme-pocket polarity in low potential cytochrome b5 of Giardia intestinalis.

    PubMed

    Yang, Zhen Alice; Pazdzior, Robert; Yee, Janet; Rafferty, Steven

    2016-05-01

    Although it lacks mitochondria and the ability to synthesize heme, the protozoan parasite Giardia intestinalis encodes several heme proteins. This includes four members of the cytochrome b5 family, three of which are of similar size to mammalian cytochromes b5 but with reduction potentials that are 140 to 180mV lower. While no structures have yet been determined for any of these proteins, homology modeling points to an increase in heme pocket polarity as a reason for their low potentials. To test this we measured the reduction potentials of four mutants of Giardia cytochrome b5 isotype-I (gCYTB5-I) in which polar residues at two candidate positions (C84, Y51) in the heme pocket were changed to nonpolar ones (C84A, C84F; Y51L, Y51F). All mutants were expressed with comparable levels of heme incorporation and had UV-visible spectra consistent with low spin bis-histidyl coordination. These mutations increased the reduction potential by 18 to 57mV and highlight the influence of C84, which is a residue unique to gCYTB5-I and whose mutation to alanine caused the largest increase. The influence of these two residues plus that of Y61 reported previously accounts for much of the reduction potential difference between gCYTB5-I and microsomal cytochrome b5. A complementary triple mutant of the latter with the hydrophilic residues found in gCYTB5-I bound heme less effectively but nonetheless had a reduction potential that was 135mV lower than wild type. PMID:27048807

  3. Oxygen reduction by lithium on model carbon and oxidized carbon structures

    SciTech Connect

    Xu, Ye; Shelton Jr, William Allison

    2011-01-01

    Li-air batteries have attracted substantial interest for their high theoretical specific energies, but the oxygen reduction reaction by Li (Li-ORR) that occurs at the carbon cathode remains poorly understood. Periodic density functional theory calculations have been performed to examine the Li-ORR on several model carbon structures, including the graphite(0001) basal plane, the (8,0) single-wall nanotube, the armchair-type edge, and a di-vacancy in the basal plane. The inertness of the basal plane limits the reversible potential of O{sub 2} reduction to 1.1 V, and slightly higher to 1.2 V on the curved nanotube. The armchair edge and di-vacancy are highly reactive and significantly oxidized at ambient conditions to various CO{sub x} groups, which are reduced by Li via redox mechanisms at 1.2-1.4 V. These CO{sub x} groups can also catalyze O{sub 2} reduction at up to 2.3 V (an overpotential of 0.4 V vs. the calculated equilibrium potential for bulk Li{sub 2}O{sub 2} formation) by chelating and stabilizing the LiO{sub 2} intermediate. The Li-ORR on graphitic carbon, if via concerted Li{sup +}/e{sup -} transfer and involving carbon, lithium, and oxygen only, is therefore expected to initiate with the smallest overpotential at under-coordinated carbon centers that are oxidized at ambient conditions.

  4. Potential Modulation of Sirtuins by Oxidative Stress

    PubMed Central

    Santos, Leonardo; Escande, Carlos; Denicola, Ana

    2016-01-01

    Sirtuins are a conserved family of NAD-dependent protein deacylases. Initially proposed as histone deacetylases, it is now known that they act on a variety of proteins including transcription factors and metabolic enzymes, having a key role in the regulation of cellular homeostasis. Seven isoforms are identified in mammals (SIRT1–7), all of them sharing a conserved catalytic core and showing differential subcellular localization and activities. Oxidative stress can affect the activity of sirtuins at different levels: expression, posttranslational modifications, protein-protein interactions, and NAD levels. Mild oxidative stress induces the expression of sirtuins as a compensatory mechanism, while harsh or prolonged oxidant conditions result in dysfunctional modified sirtuins more prone to degradation by the proteasome. Oxidative posttranslational modifications have been identified in vitro and in vivo, in particular cysteine oxidation and tyrosine nitration. In addition, oxidative stress can alter the interaction with other proteins, like SIRT1 with its protein inhibitor DBC1 resulting in a net increase of deacetylase activity. In the same way, manipulation of cellular NAD levels by pharmacological inhibition of other NAD-consuming enzymes results in activation of SIRT1 and protection against obesity-related pathologies. Nevertheless, further research is needed to establish the molecular mechanisms of redox regulation of sirtuins to further design adequate pharmacological interventions. PMID:26788256

  5. Potential Modulation of Sirtuins by Oxidative Stress.

    PubMed

    Santos, Leonardo; Escande, Carlos; Denicola, Ana

    2016-01-01

    Sirtuins are a conserved family of NAD-dependent protein deacylases. Initially proposed as histone deacetylases, it is now known that they act on a variety of proteins including transcription factors and metabolic enzymes, having a key role in the regulation of cellular homeostasis. Seven isoforms are identified in mammals (SIRT1-7), all of them sharing a conserved catalytic core and showing differential subcellular localization and activities. Oxidative stress can affect the activity of sirtuins at different levels: expression, posttranslational modifications, protein-protein interactions, and NAD levels. Mild oxidative stress induces the expression of sirtuins as a compensatory mechanism, while harsh or prolonged oxidant conditions result in dysfunctional modified sirtuins more prone to degradation by the proteasome. Oxidative posttranslational modifications have been identified in vitro and in vivo, in particular cysteine oxidation and tyrosine nitration. In addition, oxidative stress can alter the interaction with other proteins, like SIRT1 with its protein inhibitor DBC1 resulting in a net increase of deacetylase activity. In the same way, manipulation of cellular NAD levels by pharmacological inhibition of other NAD-consuming enzymes results in activation of SIRT1 and protection against obesity-related pathologies. Nevertheless, further research is needed to establish the molecular mechanisms of redox regulation of sirtuins to further design adequate pharmacological interventions. PMID:26788256

  6. Predicting reduction rates of energetic nitroaromatic compounds using calculated one-electron reduction potentials.

    PubMed

    Salter-Blanc, Alexandra J; Bylaska, Eric J; Johnston, Hayley J; Tratnyek, Paul G

    2015-03-17

    The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. Previously invoked linear free energy relationships (LFER) relating the log of the rate constant for this reaction (log(k)) and one-electron reduction potentials for the NAC (E1NAC) normalized to 0.059 V have been re-evaluated and compared to a new analysis using a (nonlinear) free-energy relationship (FER) based on the Marcus theory of outer-sphere electron transfer. For most reductants, the results are inconsistent with simple rate limitation by an initial, outer-sphere electron transfer, suggesting that the linear correlation between log(k) and E1NAC is best regarded as an empirical model. This correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of log(k) for nonenergetic NAC reduction by Fe(II) porphyrin and newly reported values of E1NAC determined using density functional theory at the M06-2X/6-311++G(2d,2p) level with the COSMO solvation model. The QSAR was then validated for energetic NACs using newly measured kinetic data for 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to other energetic NACs. PMID:25671710

  7. Electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices

    NASA Astrophysics Data System (ADS)

    He, Zhen

    The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe3O4 ) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide heterojunctions and a wide range of epitaxial metallic alloy films from the corresponding mixed metal oxides. Electrodeposition, like biomineralization, is a soft solution processing method which can produce functional materials with special properties onto conducting or semiconducting solid surfaces. Paper II in this dissertation presents the electrodeposition of cobalt-substituted magnetite (CoxFe3-xO4, 0 of cobalt-substituted magnetite (CoxFe3-xO4, 0potentially used in spintronics and memory devices. Paper III in this dissertation reports the electrodeposition of crystalline cobalt oxide (Co3O4) thin films on stainless steel and Au single-crystalline substrates. The crystalline Co3O4 thin films exhibit high catalytic activity towards the oxygen evolution reaction in an alkaline solution. A possible application of the electrodeposited Co 3O4 is the fabrication of highly active and low-cost photoanodes for photoelectrochemical water-splitting cells.

  8. Microbially Induced Reductive Dissolution of Trace Element-Rich Lacustrine Iron-Oxides

    NASA Astrophysics Data System (ADS)

    Crowe, S. A.; Kulczykci, E.; O'Neill, A. H.; Roberts, J. A.; Fowle, D. A.

    2004-12-01

    nutrient bearing phases were dissolved. It was found that during DIR many trace elements (e.g. Ni, Mn, Co, Cr, P, and Si) were redistributed between the aqueous and solid phases. However trace element release was not congruent with Fe-oxide dissolution and the maximum aqueous concentrations of Mn, and Co were observed after less than three days of incubation. The rapid release of metals, particularly Co, Mn and Ni, suggest that these elements may be present in discrete phases more readily reduced than the bulk iron (oxy)hydroxides (e.g. MnO2). Cr is initially solubilized but is subsequently removed with progressive Fe reduction. This is consistent with the reduction of aqueous Cr (VI) to Cr (III) by Fe2+. Thus, in natural Fe-oxides there is potential for significant Fe2+ re-oxidation following the release of solid phase oxidants. In summary, our experiments suggest that in lacustrine environments Fe-oxides may be reductively dissolved at higher rates than predicted from laboratory experiments using single-phase pure iron (oxy)hydroxides. The release of the macronutrient phosphorus during DIR may enable sustained reduction in carbon rich anaerobic lake sediments. Furthermore, MnO2 may place a significant role in controlling trace element cycling even in very Fe-rich sediments.

  9. Iron isotope fractionation during microbial dissimilatory iron oxide reduction in simulated Archaean seawater.

    PubMed

    Percak-Dennett, E M; Beard, B L; Xu, H; Konishi, H; Johnson, C M; Roden, E E

    2011-05-01

    The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded iron formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory iron reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) oxide substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) oxide-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. Iron isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-δ(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks. PMID:21504536

  10. Note: Rapid reduction of graphene oxide paper by glow discharge plasma

    SciTech Connect

    Bo, Zheng; Qian, Jiajing; Duan, Liangping; Qiu, Kunzan Yan, Jianhua; Cen, Kefa; Han, Zhao Jun; Ostrikov, Kostya

    2015-05-15

    This note reports on a novel method for the rapid reduction of graphene oxide (GO) paper using a glow discharge plasma reactor. Glow discharge is produced and sustained between two parallel-plate graphite electrodes at a pressure of 240 mTorr. By exposing GO paper at the junction of negative-glow and Faraday-dark area for 4 min, the oxygen-containing groups can be effectively removed (C/O ratio increases from 2.6 to 7.9), while the material integrality and flexibility are kept well. Electrochemical measurements demonstrate that the as-obtained reduced GO paper can be potentially used for supercapacitor application.

  11. Investigation on the Oxidation and Reduction of Titanium in Molten Salt with the Soluble TiC Anode

    NASA Astrophysics Data System (ADS)

    Wang, Shulan; Wan, Chaopin; Liu, Xuan; Li, Li

    2015-12-01

    To reveal the oxidation process of titanium from TiC anode and the reduction mechanism of titanium ions in molten NaCl-KCl, the polarization curve of TiC anode in molten NaCl-KCl and cyclic voltammograms of the molten salt after polarization were studied. Investigation on the polarization curve shows that titanium can be oxidized and dissociated from the TiC anode at very low potential. The cyclic voltammograms demonstrated that the reduction reaction of titanium ions in the molten salt is a one-step process. By potentiostatic electrolysis, dendritic titanium is obtained on the steel plate. The work promotes the understanding on the process of electrochemical oxidization/dissociation of titanium from TiC anode and the reduction mechanism of titanium ions in molten salt.

  12. Linking methane oxidation with perchlorate reduction: a microbial base for possible Martian life

    NASA Astrophysics Data System (ADS)

    Miller, L. G.; Carlstrom, C.; Baesman, S. M.; Coates, J. D.; Oremland, R. S.

    2011-12-01

    Recent observations of methane (CH4) and perchlorate (ClO4-) within the atmosphere and surface of Mars, respectively, provide impetus for establishing a metabolic linkage between these compounds whereby CH4 acts as an electron donor and perchlorate acts as an electron acceptor. Direct linkage through anaerobic oxidation of methane (AOM) has not been observed. However, indirect syntrophic oxygenase-dependent oxidation of CH4 with an aerobic methane oxidizer is feasible. The pathway for anaerobic dissimilatory perchlorate reduction includes 3 steps. The first 2 are sequential reductions of (1) perchlorate to chlorate and (2) chlorate to chlorite, mediated by perchlorate reductase. The third step is disproportionation of chlorite to chloride and molecular oxygen, mediated by chlorite dismutase. Utilization of thusly derived oxygen by hydrocarbon-degrading organisms in anoxic environments was first demonstrated by Coates et. al. (1998)1, however the link to aerobic methane oxidation was not examined at that time. Here, we systematically explore the potential for several species of aerobic methanotrophs to couple with chlorite during dissimilatory perchlorate reduction. In one experiment, 0.5 kPa CH4 was completely removed in one day from the headspace of combined cell suspensions of Dechloromonas agitata strain CKB and Methylococcus capsulatus in the presence of 5 mM chlorite. Oxidation of labeled 14CH4 to 14CO2 under similar conditions was later confirmed. Another experiment demonstrated complete removal of 0.2 kPa CH4 over several days by Methylobacter albus strain BG8 with strain CKB in the presence of 5 mM chlorite. Finally, we observed complete removal of 0.2 kPa CH4 in bottles containing natural soil (enriched in methanotrophs by CH4 additions over several weeks) and strain CKB and in the presence of 10 mM chlorite. This soil, collected from a pristine lake shoreline, demonstrated endogenous methane, perchlorate, chlorate and chlorite uptake. Other soil and

  13. Microbial oxidation and reduction of manganese: consequences in groundwater and applications.

    PubMed

    Gounot, A M

    1994-08-01

    In the natural environment, manganese is found as reduced soluble or adsorbed Mn(II) and insoluble Mn(III) and Mn(IV) oxides. Mn oxidation has been reported in various microorganisms. Several possible pathways, indirect or direct, have been proposed. A wider variety of Mn-reducing microorganisms, from highly aerobic to strictly anaerobic, has been described. The mechanisms of Mn reduction can be either an indirect process resulting from interactions with organic or inorganic compounds, or a direct enzymatic (electron-transfer) reaction. The role of microorganisms in Mn cycle is now well demonstrated by various methods in superficial natural environments, and research has been initiated on subsurface sediments. Observations in vivo (Rhône valley) and under in vitro suggested that bacterial activities are the main processes that promote manganese evolution and migration in shallow aquifers. After the building of hydroelectric dams, the stream of the Rhône was modified, giving rise to mud deposition on the bank. In the mud, bacteria are stimulated by the high organic content and consume oxygen. The redox potential drops. The manganese oxides previously formed under aerobic conditions are reduced and soluble manganese (Mn(II)) migrates into the aquifer. If the subsurface sediments are coarse-grained, the aquifer is well aerated, allowing the re-oxidation of Mn(II) by the oligotrophic attached bacteria in aquifer sediments. If the aquifer is confined, aeration is not sufficient for Mn-reoxidation. Mn(II) remains in a reduced state and migrates to the wells. Furthermore, the presence of organic matter in subsurface sediments results in the reduction of previously formed Mn oxides. Pseudo-amorphous manganese oxides, which were probably recently formed by bacteria, are more readily reduced than old crystalline manganese oxides. Although the concentrations of soluble manganese found in groundwaters are not toxic, it still is a problem since its oxidation results in

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

    SciTech Connect

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

    2002-09-16

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

  15. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  16. Electrochemical investigation of polyhalide ion oxidation-reduction on carbon nanotube electrodes for redox flow batteries

    SciTech Connect

    Shao, Yuyan; Engelhard, Mark H.; Lin, Yuehe

    2009-10-01

    Polyhalide ions (Br-/BrCl2-) are an important redox couple for redox flow batteries. The oxidation-reduction behavior of polyhalide ions on a carbon nanotube (CNT) electrode has been investigated with cyclic voltammetry and electrochemical impedance spectroscopy. The onset oxidation potential of Br-/BrCl2- is negatively shifted by >100 mV, and the redox current peaks are greatly enhanced on a CNT electrode compared with that on the most widely-used graphite electrode. The reaction resistance of the redox couple (Br-/BrCl2-) is decreased on a CNT electrode. The redox reversibility is increased on a CNT electrode even though it still needs further improvement. CNT is a promising electrode material for redox flow batteries.

  17. Phosphonated nanocelluloses from sequential oxidative-reductive treatment-Physicochemical characteristics and thermal properties.

    PubMed

    Sirviö, Juho Antti; Hasa, Tapani; Ahola, Juha; Liimatainen, Henrikki; Niinimäki, Jouko; Hormi, Osmo

    2015-11-20

    Nanocellulosic materials with good thermal stability are highly desirable for applications, such as reinforcement and filler agents in composites. In the present work, phosphonated cellulose was utilized to obtain nanocelluloses with good thermal stability and potential intumescent properties. Phosphonated cellulose was synthetized from birch pulp via sequential periodate oxidation and reductive amination using a bisphosphonate group-containing amine, sodium alendronate, as a phosphonating reagent. After high-pressure homogenization, bisphosphonate cellulose nanofibres or nanocrystals were obtained, depending on the initial oxidation degree. Nanofibres had a typical diameter of 3.8nm and length of several micrometers, whereas nanocrystals exhibited a width of about 6nm and an average length of 103-129nm. All nanocelluloses exhibited cellulose I crystalline structures and high transparency in water solutions. Phosphonated nanocelluloses exhibited good thermal stability and a greater amount of residual char was formed at 700°C compared to birch pulp and mechanically produced, non-chemically modified NFC. PMID:26344310

  18. Simulation of catalytic oxidation and selective catalytic NOx reduction in lean-exhaust hybrid vehicles

    SciTech Connect

    Gao, Zhiming; Daw, C Stuart; Chakravarthy, Veerathu K

    2012-01-01

    We utilize physically-based models for diesel exhaust catalytic oxidation and urea-based selective catalytic NOx reduction to study their impact on drive cycle performance of hypothetical light-duty diesel powered hybrid vehicles. The models have been implemented as highly flexible SIMULINK block modules that can be used to study multiple engine-aftertreatment system configurations. The parameters of the NOx reduction model have been adjusted to reflect the characteristics of Cu-zeolite catalysts, which are of widespread current interest. We demonstrate application of these models using the Powertrain System Analysis Toolkit (PSAT) software for vehicle simulations, along with a previously published methodology that accounts for emissions and temperature transients in the engine exhaust. Our results illustrate the potential impact of DOC and SCR interactions for lean hybrid electric and plug-in hybrid electric vehicles.

  19. Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution.

    PubMed

    Nancucheo, Ivan; Grail, Barry M; Hilario, Felipe; du Plessis, Chris; Johnson, D Barrie

    2014-01-01

    An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined. PMID:24687752

  20. Microbial reduction of graphene oxide by Escherichia coli: a green chemistry approach.

    PubMed

    Gurunathan, Sangiliyandi; Han, Jae Woong; Eppakayala, Vasuki; Kim, Jin-Hoi

    2013-02-01

    Graphene and graphene related materials are an important area of research in recent years due to their unique properties. The extensive industrial application of graphene and related compounds has led researchers to devise novel and simple methods for the synthesis of high quality graphene. In this paper, we developed an environment friendly, cost effective, simple method and green approaches for the reduction of graphene oxide (GO) using Escherichia coli biomass. In biological method, we can avoid use of toxic and environmentally harmful reducing agents commonly used in the chemical reduction of GO to obtain graphene. The biomass of E. coli reduces exfoliated GO to graphene at 37°C in an aqueous medium. The E. coli reduced graphene oxide (ERGO) was characterized with UV-visible absorption spectroscopy, particle analyzer, high resolution X-ray diffractometer, scanning electron microscopy and Raman spectroscopy. Besides the reduction potential, the biomass could also play an important role as stabilizing agent, in which synthesized graphene exhibited good stability in water. This method can open up the new avenue for preparing graphene in cost effective and large scale production. Our findings suggest that GO can be reduced by simple eco-friendly method by using E. coli biomass to produce water dispersible graphene. PMID:23107955

  1. Electron Shuttles Enhance Anaerobic Ammonium Oxidation Coupled to Iron(III) Reduction.

    PubMed

    Zhou, Guo-Wei; Yang, Xiao-Ru; Li, Hu; Marshall, Christopher W; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

    2016-09-01

    Anaerobic ammonium oxidation coupled to iron(III) reduction, termed Feammox, is a newly discovered nitrogen cycling process. However, little is known about the roles of electron shuttles in the Feammox reactions. In this study, two forms of Fe(III) (oxyhydr)oxide ferrihydrite (ex situ ferrihydrite and in situ ferrihydrite) were used in dissimilatory Fe(III) reduction (DIR) enrichments from paddy soil. Evidence for Feammox in DIR enrichments was demonstrated using the (15)N-isotope tracing technique. The extent and rate of both the (30)N2-(29)N2 and Fe(II) formation were enhanced when amended with electron shuttles (either 9,10-anthraquinone-2,6-disulfonate (AQDS) or biochar) and further simulated when these two shuttling compounds were combined. Although the Feammox-associated Fe(III) reduction accounted for only a minor proportion of total Fe(II) formation compared to DIR, it was estimated that the potentially Feammox-mediated N loss (0.13-0.48 mg N L(-1) day(-1)) was increased by 17-340% in the enrichments by the addition of electron shuttles. The addition of electron shuttles led to an increase in the abundance of unclassified Pelobacteraceae, Desulfovibrio, and denitrifiers but a decrease in Geobacter. Overall, we demonstrated a stimulatory effect of electron shuttles on Feammox that led to higher N loss, suggesting that electron shuttles might play a crucial role in Feammox-mediated N loss from soils. PMID:27494694

  2. Treatment of halogenated phenolic compounds by sequential tri-metal reduction and laccase-catalytic oxidation.

    PubMed

    Dai, Yunrong; Song, Yonghui; Wang, Siyu; Yuan, Yu

    2015-03-15

    Halogenated phenolic compounds (HPCs) are exerting negative effects on human beings and ecological health. Zero-valence metal reduction can dehalogenate HPCs rapidly but cannot mineralize them. Enzymatic catalysis can oxidize phenolic compounds but fails to dehalogenate efficiently, and sometimes even produces more toxic products. In this study, [Fe|Ni|Cu] tri-metallic reduction (TMR) and laccase-catalytic oxidation (LCO) processes were combined to sequentially remove HPCs, including triclosan, tetrabromobisphenol A, and 2-bromo-4-fluorophenol in water. The kinetics, pH and temperature dependences of TMR and LCO were obtained. The detailed TMR, LCO, and TMR-LCO transformation pathways of three HPCs were well described based on the identification of intermediate products and frontier molecular orbitals (FMOs) theory. The results showed that the two-stage process worked synergically: TMR that reductively dehalogenated HPCs followed by LCO that completely removed dehalogenated products. TMR was proven to not only improve biodegradability of HPCs but also reduce the yield of potential carcinogenic by-products. Furthermore, a TMR-LCO flow reactor was assembled and launched for 256 h, during which >95% HPCs and >75% TOC were removed. Meanwhile, monitored by microorganism indicators, 83.2%-92.7% acute toxicity of HPCs was eliminated, and the genotoxicity, produced by LCO, was also avoided by using TMR as pretreatment process. PMID:25596562

  3. Reductions in kinesin expression are associated with nitric oxide-induced axonal damage

    PubMed Central

    Redondo, Juliana; Hares, Kelly; Wilkins, Alastair; Scolding, Neil; Kemp, Kevin

    2015-01-01

    Axonal injury is often characterized by axonal transport defects and abnormal accumulation of intra-axonal components. Nitric oxide (NO) has a key role in mediating inflammatory axonopathy in many neurodegenerative diseases, but little is known about how nitrosative/oxidative stress affects axonal transport or whether reductions in kinesin superfamily protein (KIF) expression correlate with axon pathology. KIFs are molecular motors that have a key role in axonal and dendritic transport, and impairment of these mechanisms has been associated with a number of neurological disorders. This study shows that rat cortical neurons exposed to NO display both a time-dependent decrease in KIF gene/protein expression and neurofilament phosphorylation in addition to a reduction in axonal length and neuronal survival. Because mesenchymal stem cells (MSCs) represent a promising therapeutic candidate for neuronal/axonal repair, this study analyzes the capacity of MSCs to protect neurons and axonal transport mechanisms from NO damage. Results show that coculture of MSCs with NO-exposed neurons results in the preservation of KIF expression, axonal length, and neuronal survival. Altogether, these results suggest a potential mechanism involved in the disruption of axonal transport and abnormal accumulation of proteins in axons during nitrosative insult. We hypothesize that impaired axonal transport contributes, per se, to progression of injury and provide further evidence of the therapeutic potential of MSCs for neurodegenerative disorders. © 2015 The Authors. Journal of Neuroscience Research Published by Wiley Periodicals, Inc. PMID:25639260

  4. Reductions in kinesin expression are associated with nitric oxide-induced axonal damage.

    PubMed

    Redondo, Juliana; Hares, Kelly; Wilkins, Alastair; Scolding, Neil; Kemp, Kevin

    2015-06-01

    Axonal injury is often characterized by axonal transport defects and abnormal accumulation of intra-axonal components. Nitric oxide (NO) has a key role in mediating inflammatory axonopathy in many neurodegenerative diseases, but little is known about how nitrosative/oxidative stress affects axonal transport or whether reductions in kinesin superfamily protein (KIF) expression correlate with axon pathology. KIFs are molecular motors that have a key role in axonal and dendritic transport, and impairment of these mechanisms has been associated with a number of neurological disorders. This study shows that rat cortical neurons exposed to NO display both a time-dependent decrease in KIF gene/protein expression and neurofilament phosphorylation in addition to a reduction in axonal length and neuronal survival. Because mesenchymal stem cells (MSCs) represent a promising therapeutic candidate for neuronal/axonal repair, this study analyzes the capacity of MSCs to protect neurons and axonal transport mechanisms from NO damage. Results show that coculture of MSCs with NO-exposed neurons results in the preservation of KIF expression, axonal length, and neuronal survival. Altogether, these results suggest a potential mechanism involved in the disruption of axonal transport and abnormal accumulation of proteins in axons during nitrosative insult. We hypothesize that impaired axonal transport contributes, per se, to progression of injury and provide further evidence of the therapeutic potential of MSCs for neurodegenerative disorders. PMID:25639260

  5. Particulate Matter Oxidative Potential from Waste Transfer Station Activity

    PubMed Central

    Godri, Krystal J.; Duggan, Sean T.; Fuller, Gary W.; Baker, Tim; Green, David; Kelly, Frank J.; Mudway, Ian S.

    2010-01-01

    Background Adverse cardiorespiratory health is associated with exposure to ambient particulate matter (PM). The highest PM concentrations in London occur in proximity to waste transfer stations (WTS), sites that experience high numbers of dust-laden, heavy-duty diesel vehicles transporting industrial and household waste. Objective Our goal was to quantify the contribution of WTS emissions to ambient PM mass concentrations and oxidative potential. Methods PM with a diameter < 10 μm (PM10) samples were collected daily close to a WTS. PM10 mass concentrations measurements were source apportioned to estimate local versus background sources. PM oxidative potential was assessed using the extent of antioxidant depletion from a respiratory tract lining fluid model. Total trace metal and bioavailable iron concentrations were measured to determine their contribution to PM oxidative potential. Results Elevated diurnal PM10 mass concentrations were observed on all days with WTS activity (Monday–Saturday). Variable PM oxidative potential, bioavailable iron, and total metal concentrations were observed on these days. The contribution of WTS emissions to PM at the sampling site, as predicted by microscale wind direction measurements, was correlated with ascorbate (r = 0.80; p = 0.030) and glutathione depletion (r = 0.76; p = 0.046). Increased PM oxidative potential was associated with aluminum, lead, and iron content. Conclusions PM arising from WTS activity has elevated trace metal concentrations and, as a consequence, increased oxidative potential. PM released by WTS activity should be considered a potential health risk to the nearby residential community. PMID:20368130

  6. Reduction of Nitrogen Oxide Emissions for lean Burn Engine Technology

    SciTech Connect

    McGill, R.N.

    1998-08-04

    Lean-burn engines offer the potential for significant fuel economy improvements in cars and trucks, perhaps the next great breakthrough in automotive technology that will enable greater savings in imported petroleum. The development of lean-burn engines, however, has been an elusive goal among automakers because of the emissions challenges associated with lead-burn engine technology. Presently, cars operate with sophisticated emissions control systems that require the engine's air-fuel ratio to be carefully controlled around the stoichiometric point (chemically correct mixture). Catalysts in these systems are called "three-way" catalysts because they can reduce hydrocarbon, carbon monoxide, and nitrogen oxide emissions simultaneously, but only because of the tight control of the air-fuel ratio. The purpose of this cooperative effort is to develop advanced catalyst systems, materials, and necessary engine control algorithms for reducing NOX emissions in oxygen-rich automotive exhaust (as with lean-burn engine technology) to meet current and near-future mandated Clean Air Act standards. These developments will represent a breakthrough in both emission control technology and automobile efficiency. The total project is a joint effort among five national laboratories, together with US CAR. The role of Lockheed-Martin Energy Systems in the total project is two fold: characterization of catalyst performance through laboratory evaluations from bench-scale flow reactor tests to engine laboratory tests of full-scale prototype catalysts, and microstructural characterization of catalyst material before and after test stand and/or engine testing.

  7. Computational studies of polysiloxanes : oxidation potentials and decomposition reactions.

    SciTech Connect

    Assary, R. S.; Curtiss, L. A.; Redfern, P. C.; Zhang, Z.; Amine, K.

    2011-06-23

    Silicon-containing solvents have tremendous potential for application as electrolytes for electrical energy storage devices such as lithium-ion (air) batteries and supercapacitors. Quantum chemical methods were employed to investigate trends in oxidation potentials and decomposition reactions of a series of polysiloxanes. Various electron-donating and -withdrawing substituents can be used to tune the oxidation potential in shorter chain siloxanes but not in longer ones. Decomposition reactions of siloxanes in their oxidized states were investigated and compared against their carbon analogues. These studies suggest that the Si-O group provides added stability for siloxanes over their carbon analogues. Computational studies have also been performed for various disiloxanes and siloxanes with spacer groups to understand their thermochemical stability and oxidation potentials.

  8. Method For Selective Catalytic Reduction Of Nitrogen Oxides

    DOEpatents

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

  9. Method for selective catalytic reduction of nitrogen oxides

    DOEpatents

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

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

    NASA Astrophysics Data System (ADS)

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

    2002-09-01

    The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO 2], bixbyite [Mn 2O 3] and K +-birnessite [K 4Mn 14O 27 · 8H 2O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO 2[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH] 3) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO 2(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.

  11. H{sub 2} from biosyngas via iron reduction and oxidation

    SciTech Connect

    Straus, J.; Terry, P.

    1995-09-01

    The production of hydrogen from the steam-oxidation of iron is a long-known phenomenon. The rise in interest in the production and storage of hydrogen justifies the examination of this process (and of the reverse process, the reduction of iron oxide) for commercial use. Under NREL subcontract ZAR-4-13294-02, a process simulation program was developed and used as a design tool to analyze various configurations of the iron-hydrogen purification/storage scheme. Specifically, analyses were performed to determine the effectiveness of this scheme in conjunction with biomass-derived gasified fuel streams (biosyngas). The results of the computer simulations led to a selection of a two-stage iron oxide reduction process incorporating interstage water and CO{sub 2} removal. Thermal analysis shows that the iron-hydrogen process would yield essentially the same quantity of clean hydrogen per unit of biomass as the conventional route. The iron-hydrogen process benefits from the excellent match potentially achievable between the otherwise-unusable energy fraction in the off-gas of the reduction reactor and the parasitic thermal, mechanical and electrical energy needs of some typical gasifier systems. The program simulations and economic analysis suggest that clean hydrogen from biomass feedstock could cost about 20% less via the iron-hydrogen method than by conventional methods of purification (using the same feedstock). Cost analyses show that lower capital costs would be incurred in generating clean hydrogen by utilizing this approach, especially in response to the fluctuating demand profile of a utility.

  12. Improved free energy profile for reduction of NO in cytochrome c dependent nitric oxide reductase (cNOR).

    PubMed

    Blomberg, Margareta R A; Siegbahn, Per E M

    2016-07-15

    Quantum chemical calculations play an essential role in the elucidation of reaction mechanisms for redox-active metalloenzymes. For example, the cleavage and the formation of covalent bonds can usually not be described only on the basis of experimental information, but can be followed by the calculations. Conversely, there are properties, like reduction potentials, which cannot be accurately calculated. Therefore, computational and experimental data has to be carefully combined to obtain reliable descriptions of entire catalytic cycles involving electron and proton uptake from donors outside the enzyme. Such a procedure is illustrated here, for the reduction of nitric oxide (NO) to nitrous oxide and water in the membrane enzyme, cytochrome c dependent nitric oxide reductase (cNOR). A surprising experimental observation is that this reaction is nonelectrogenic, which means that no energy is conserved. On the basis of hybrid density functional calculations a free energy profile for the entire catalytic cycle is obtained, which agrees much better with experimental information on the active site reduction potentials than previous ones. Most importantly the energy profile shows that the reduction steps are endergonic and that the entire process is rate-limited by high proton uptake barriers during the reduction steps. This result implies that, if the reaction were electrogenic, it would become too slow when the gradient is present across the membrane. This explains why this enzyme does not conserve any of the free energy released. © 2016 Wiley Periodicals, Inc. PMID:27130561

  13. Comparative studies on single-layer reduced graphene oxide films obtained by electrochemical reduction and hydrazine vapor reduction

    PubMed Central

    2012-01-01

    The comparison between two kinds of single-layer reduced graphene oxide (rGO) sheets, obtained by reduction of graphene oxide (GO) with the electrochemical method and hydrazine vapor reduction, referred to as E-rGO and C-rGO, respectively, is systematically studied. Although there is no morphology difference between the E-rGO and C-rGO films adsorbed on solid substrates observed by AFM, the reduction process to obtain the E-rGO and C-rGO films is quite different. In the hydrazine vapor reduction, the nitrogen element is incorporated into the obtained C-rGO film, while no additional element is introduced to the E-rGO film during the electrochemical reduction. Moreover, Raman spectra show that the electrochemical method is more effective than the hydrazine vapor reduction method to reduce the GO films. In addition, E-rGO shows better electrocatalysis towards dopamine than does C-rGO. This study is helpful for researchers to understand these two different reduction methods and choose a suitable one to reduce GO based on their experimental requirements. PMID:22373422

  14. DNAPL mass transfer and permeability reduction during in situ chemical oxidation with permanganate

    NASA Astrophysics Data System (ADS)

    Li, X. David; Schwartz, Franklin W.

    2004-03-01

    This study utilized a series of laboratory experiments to examine the DNAPL mass removal rate and permeability reduction during ISCO using permanganate (MnO4-). Results show that MnO4- oxidation is effective in removing residual DNAPL from a porous medium. The DNAPL mass removal rate correlated positively with both the hydraulic stress and the oxidant load. A power relationship model of DNAPL mass removal under ISCO was proposed. Results also show that oxidation by-products CO2(g) and Mn oxide can cause pore plugging and flow by-passing. The reduction in hydraulic conductivity due to the Mn oxide precipitates was quantified. Hydraulic conductivity reduction as high as 80% was observed for oxidizing a small quantity of TCE.

  15. Reduction of Soluble Iron and Reductive Dissolution of Ferric Iron-Containing Minerals by Moderately Thermophilic Iron-Oxidizing Bacteria

    PubMed Central

    Bridge, Toni A. M.; Johnson, D. Barrie

    1998-01-01

    Five moderately thermophilic iron-oxidizing bacteria, including representative strains of the three classified species (Sulfobacillus thermosulfidooxidans, Sulfobacillus acidophilus, and Acidimicrobium ferrooxidans), were shown to be capable of reducing ferric iron to ferrous iron when they were grown under oxygen limitation conditions. Iron reduction was most readily observed when the isolates were grown as mixotrophs or heterotrophs with glycerol as an electron donor; in addition, some strains were able to couple the oxidation of tetrathionate to the reduction of ferric iron. Cycling of iron between the ferrous and ferric states was observed during batch culture growth in unshaken flasks incubated under aerobic conditions, although the patterns of oxidoreduction of iron varied in different species of iron-oxidizing moderate thermophiles and in strains of a single species (S. acidophilus). All three bacterial species were able to grow anaerobically with ferric iron as a sole electron acceptor; the growth yields correlated with the amount of ferric iron reduced when the isolates were grown in the absence of oxygen. One of the moderate thermophiles (identified as a strain of S. acidophilus) was able to bring about the reductive dissolution of three ferric iron-containing minerals (ferric hydroxide, jarosite, and goethite) when it was grown under restricted aeration conditions with glycerol as a carbon and energy source. The significance of iron reduction by moderately thermophilic iron oxidizers in both environmental and applied contexts is discussed. PMID:9603832

  16. Reduction of nitric oxide emissions from a combustor

    NASA Technical Reports Server (NTRS)

    Craig, R. A.; Pritchard, H. O. (Inventor)

    1980-01-01

    A turbojet combustor and method for controlling nitric oxide emissions by employing successive combustion zones is described. After combustion of an initial portion of the fuel in a primary combustion zone, the combustion products of the primary zone are combined with the remaining portion of fuel and additional plenum air and burned in a secondary combustion zone under conditions that result in low nitric oxide emissions. Low nitric oxide emissions are achieved by a novel turbojet combustor arrangement which provides flame stability by allowing stable combustion to be accompanied by low nitric oxide emissions resulting from controlled fuel-lean combustion (ignited by the emission products from the primary zone) in a secondary combustion zone at a lower combustion temperature resulting in low emission of nitric oxide.

  17. Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations

    SciTech Connect

    Tufano, K.J.; Benner, S.G.; Mayer, K.U.; Marcus, M.A.; Nico, P.S.; Fendorf, S.

    2009-06-15

    There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealized micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in

  18. Exoelectrogens Leading to Precise Reduction of Graphene Oxide by Flexibly Switching Their Environment during Respiration.

    PubMed

    Bansal, Prerna; Doshi, Sejal; Panwar, Ajay S; Bahadur, Dhirendra

    2015-09-23

    Reduced graphene oxide (RGO) has been prepared by a simple, cost-effective, and green route. In this work, graphene oxide (GO) has been reduced using Gram-negative facultative anaerobe S. dysenteriae, having exogenic properties of electron transfer via electron shuttling. Apparently, different concentrations of GO were successfully reduced with almost complete mass recovery. An effective role of lipopolysaccharide has been observed while comparing RGO reduced by S. dysenteriae and S. aureus. It was observed that the absence of lipopolysaccharide in Gram-positive S. aureus leads to a disrupted cell wall and that S.aureus could not survive in the presence of GO, leading to poor and inefficient reduction of GO, as shown in our results. However, S. dysenteriae having an outer lipopolysaccharide layer on its cell membrane reduced GO efficiently and the reduction process was extracellular for it. RGO prepared in our work has been characterized by X-ray diffraction, ζ potential, X-ray photoelectron spectroscopy, and Raman spectroscopy techniques, and the results were found to be in good agreement with those of chemically reduced GO. As agglomeration of RGO is the major issue to overcome while chemically reducing GO, we observed that RGO prepared by a bacterial route in our work has ζ potential value of -26.62 mV, good enough to avoid restacking of RGO. The role of exoelectrogens in electron transfer in the extracellular space has been depicted. Toxin released extracellularly during the process paves the way for reduction of GO due to its affinity towards oxygen. PMID:26288348

  19. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    spinel Mn3O4) for smaller particle size and in the presence of surface hydration. Chemisorption of water onto anhydrous nanophase Mn2O 3 surfaces promotes rapidly reversible redox phase changes at room temperature as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Water adsorption microcalorimetry (in situ) at room temperature measured the strongly exothermic integral enthalpy of water adsorption (-103.5 kJ/mol) and monitored the energetics of the redox phase transformation. Hydration-driven redox transformation of anhydrous nanophase Mn(III) 2O3, (high surface enthalpy of anhydrous surfaces 1.77 +/- 0.10 J/m2) to Mn(II,III)3O4 (lower surface enthalpy 0.96 +/- 0.08 J/m2) occurred during the first few doses of water vapor. Surface reduction of nanoparticle bixbyite (Mn 2O3) to hausmannite (Mn3O4) occurs under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Layered structure manganese oxides contain alkali or alkaline earth cations and water, are generally fine-grained, and have considerable thermodynamic stability. The surface enthalpies (SE) of layered and tunnel structure complex manganese oxides are significantly lower than those of the binary manganese oxide phases. The SE for hydrous surfaces and overall manganese average oxidation state (AOS) (value in parentheses) are: cryptomelane 0.77 +/- 0.10 J/m 2 (3.78), sodium birnessite 0.69 +/- 0.13 J/m2 (3.56), potassium birnessite 0.55 +/- 0.11 J/m2 (3.52), and calcium birnessite 0.41 +/- 0.11 J/m2 (3.50). Surface enthalpies of hydrous surfaces of the calcium manganese oxide nanosheets are: deltaCa 0.39MnO2.3nH2O 0.75 +/- 0.10 J/m2 (3.89) and deltaCa0.43MnO2.3nH2O 0.57 +/- 0.12 J/m2 (3.68). The surface enthalpy of the complex manganese oxides appears to decrease with decreasing manganese average oxidation state, that is, with greater mixed valence manganese (Mn 3+/4+). Low surface energy suggests loose

  20. Electronic properties of epitaxial cerium oxide films during controlled reduction and oxidation studied by resonant inelastic X-ray scattering.

    PubMed

    Gasperi, Gabriele; Amidani, Lucia; Benedetti, Francesco; Boscherini, Federico; Glatzel, Pieter; Valeri, Sergio; Luches, Paola

    2016-07-27

    We investigated the evolution of the electronic structure of cerium oxide ultrathin epitaxial films during reduction and oxidation processes using resonant inelastic X-ray scattering at the Ce L3 absorption edge, a technique sensitive to the electronic configurations at the 4f levels and in the 5d band thanks to its high energy resolution. We used thermal treatments in high vacuum and in oxygen partial pressure to induce a controlled and reversible degree of reduction in cerium oxide ultrathin epitaxial films of different thicknesses. Two dominant spectral components contribute to the measured spectra at the different degrees of oxidation/reduction. In ultrathin films a modification of the electronic properties associated with platinum substrate proximity and with dimensionality is identified. The different electronic properties induce a higher reducibility in ultrathin films, ascribed to a decrease of the surface oxygen vacancy formation energy. PMID:27405957

  1. Electrochemical Potential Gradient as a Quantitative in Vitro Test Platform for Cellular Oxidative Stress.

    PubMed

    Bryant, Carson; Atha, Donald; Reipa, Vytas

    2016-01-01

    Oxidative stress in a biological system is often defined as a redox imbalance within cells or groups of cells within an organism. Reductive-oxidative (redox) imbalances in cellular systems have been implicated in several diseases, such as cancer. To better understand the redox environment within cellular systems, it is important to be able to characterize the relationship between the intensity of the oxidative environment, characterized by redox potential, and the biomolecular consequences of oxidative damage. In this study, we show that an in situ electrochemical potential gradient can serve as a tool to simulate exogenous oxidative stress in surface-attached mammalian cells. A culture plate design, which permits direct imaging and analysis of the cell viability, following exposure to a range of solution redox potentials, was developed. The in vitro oxidative stress test vessel consists of a cell growth flask fitted with two platinum electrodes that support a direct current along the flask bottom. The applied potential span and gradient slope can be controlled by adjusting the constant current magnitude across the vessel with spatially localized media potentials measured with a sliding reference electrode. For example, the viability of Chinese Hamster Ovary cells under a gradient of redox potentials indicated that cell death was initiated at approximately 0.4 V vs. standard hydrogen electrode (SHE) media potential and this potential could be modified with antioxidants. This experimental platform may facilitate studies of oxidative stress characteristics on different types of cells by enabling imaging live cell cultures that have been exposed to a gradient of exogenous redox potentials. PMID:27409641

  2. Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the

  3. 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.

  4. Effects of dissimilatory sulfate reduction on FeIII (hydr)oxide reduction and microbial community development

    NASA Astrophysics Data System (ADS)

    Kwon, Man Jae; Boyanov, Maxim I.; Antonopoulos, Dionysios A.; Brulc, Jennifer M.; Johnston, Eric R.; Skinner, Kelly A.; Kemner, Kenneth M.; O'Loughlin, Edward J.

    2014-03-01

    Although dissimilatory iron and sulfate reduction (DIR and DSR) profoundly affect the biogeochemical cycling of C, Fe, and S in subsurface systems, the dynamics of DIR and DSR in the presence of both FeIII (hydr)oxides and sulfate have not been well-studied with mixed microbial populations. This study examined the response of native microbial communities in subsurface sediment from the U.S. Department of Energy’s Integrated Field Research Challenge site in Rifle, CO to the availability of sulfate and specific FeIII (hydr)oxide minerals in experimental systems containing lactate as the electron donor, with ferrihydrite, goethite, or lepidocrocite and high (10.2 mM) or low (0.2 mM) sulfate as electron acceptors. We observed rapid fermentation of lactate to acetate and propionate. FeIII reduction was slow and limited in the presence of low-sulfate, but the extent of FeIII reduction increased more than 10 times with high-sulfate amendments. Furthermore, the extent of FeIII reduction was higher in ferrihydrite or lepidocrocite incubations than in goethite incubations. Propionate produced during fermentation of lactate was used as the electron donor for DSR. The concurrence of sulfate reduction and FeII production suggests that FeII production was driven primarily by reduction of FeIII by biogenic sulfide. X-ray absorption fine-structure analysis confirmed the formation of ferrous sulfide and the presence of O-coordinated ferrous species. 16S rRNA-based microbial community analysis revealed the development of distinct communities with different FeIII (hydr)oxides. These results highlight the highly coupled nature of C, Fe, and S biogeochemical cycles during DIR and DSR and provide new insight into the effects of electron donor utilization, sulfate concentration, and the presence of specific FeIII (hydr)oxide phases on microbial community development.

  5. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    USGS Publications Warehouse

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

  6. SPATIAL AND TEMPORAL GRADIENTS IN AQUIFER OXIDATION- REDUCTION CONDITIONS

    EPA Science Inventory

    The study was undertaken to identify principal oxidizing and reducing chemical species in groundwater with the goal of determining the utility of platinum electrode (Eh) measurements to characterize subsurface redox conditions. Serial measurements of Eh and groundwater analyses w...

  7. Fluidized reduction of oxides on fine metal powders without sintering

    NASA Technical Reports Server (NTRS)

    Hayashi, T.

    1985-01-01

    In the process of reducing extremely fine metal particles (av. particle size or = 1000 angstroms) covered with an oxide layer, the metal particles are fluidized by a gas flow contg. H, heated, and reduced. The method uniformly and easily reduces surface oxide layers of the extremely fine metal particles without causing sintering. The metal particles are useful for magnetic recording materials, conductive paste, powder metallurgy materials, chem. reagents, and catalysts.

  8. Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions.

    PubMed

    Mel, Abdel-Aziz El; Tessier, Pierre-Yves; Buffiere, Marie; Gautron, Eric; Ding, JunJun; Du, Ke; Choi, Chang-Hwan; Konstantinidis, Stephanos; Snyders, Rony; Bittencourt, Carla; Molina-Luna, Leopoldo

    2016-06-01

    Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage. PMID:27061060

  9. WORKSHOP ON MONITORING OXIDATION-REDUCTION PROCESSES FOR GROUND-WATER RESTORATION

    EPA Science Inventory

    Redox conditions are among the most important parameters for controlling contaminant transport and fate in ground-water systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting solubility, rea...

  10. Developing Investigation Skills in an Introductory Multistep Synthesis Using Fluorene Oxidation and Reduction

    ERIC Educational Resources Information Center

    Stocksdale, Mark G; Pointer, Roy D; Benson, Barret W.; Fletcher, Steven E. S.; Henry, Ian; Ogren, Paul J.; Berg, Michael A. G.

    2004-01-01

    A two-step oxidation-reduction sequence that incorporates several important aspects of synthesis into introductory organic chemistry laboratories is described. This experiment is an excellent vehicle for introducing elements of discovery and intermediate yield improvement strategies.

  11. Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

    SciTech Connect

    Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA; Co-Principal Investigator: Jeff Terry, Illinois Institute of Technology, Chicago, IL

    2008-05-12

    objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.

  12. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles.

    PubMed

    Byrne, James M; van der Laan, Gerrit; Figueroa, Adriana I; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M; Kappler, Andreas

    2016-01-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100-200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments. PMID:27492680

  13. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    PubMed Central

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-01-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments. PMID:27492680

  14. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    NASA Astrophysics Data System (ADS)

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-08-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments.

  15. Copper Oxidation/Reduction in Water and Protein: Studies with DFTB3/MM and VALBOND Molecular Dynamics Simulations.

    PubMed

    Jin, Haiyun; Goyal, Puja; Das, Akshaya Kumar; Gaus, Michael; Meuwly, Markus; Cui, Qiang

    2016-03-01

    We apply two recently developed computational methods, DFTB3 and VALBOND, to study copper oxidation/reduction processes in solution and protein. The properties of interest include the coordination structure of copper in different oxidation states in water or in a protein (plastocyanin) active site, the reduction potential of the copper ion in different environments, and the environmental response to copper oxidation. The DFTB3/MM and VALBOND simulation results are compared to DFT/MM simulations and experimental results whenever possible. For a copper ion in aqueous solution, DFTB3/MM results are generally close to B3LYP/MM with a medium basis, including both solvation structure and reduction potential for Cu(II); for Cu(I), however, DFTB3/MM finds a two-water coordination, similar to previous Born-Oppenheimer molecular dynamics simulations using BLYP and HSE, whereas B3LYP/MM leads to a tetrahedron coordination. For a tetraammonia copper complex in aqueous solution, VALBOND and DFTB3/MM are consistent in terms of both structural and dynamical properties of solvent near copper for both oxidation states. For copper reduction in plastocyanin, DFTB3/MM simulations capture the key properties of the active site, and the computed reduction potential and reorganization energy are in fair agreement with experiment, especially when the periodic boundary condition is used. Overall, the study supports the value of VALBOND and DFTB3(/MM) for the analysis of fundamental copper redox chemistry in water and protein, and the results also help highlight areas where further improvements in these methods are desirable. PMID:26624804

  16. Conceptual difficulties experienced by senior high school students of electrochemistry: Electric circuits and oxidation-reduction equations

    NASA Astrophysics Data System (ADS)

    Garnett, Pamela J.; Treagust, David F.

    The purpose of this research was to investigate students' understanding of electrochemistry following a course of instruction. A list of conceptual and propositional knowledge statements was formulated to identify the knowledge base necessary for students to understand electric circuits and oxidation-reduction equations. The conceptual and propositional knowledge statements provided the framework for the development of a semistructured interview protocol which was administered to 32 students in their final year of high school chemistry. The interview questions about electric circuits revealed that several students in the sample were confused about the nature of electric current both in metallic conductors and in electrolytes. Students studying both physics and chemistry were more confused about current flow in metallic conductors than students who were only studying chemistry. In the section of the interview which focused on oxidation and reduction, many students experienced problems in identifying oxidation-reduction equations. Several misconceptions relating to the inappropriate use of definitions of oxidation and reduction were identified. The data illustrate how students attempted to make sense of the concepts of electrochemistry with the knowledge they had already developed or constructed. The implications of the research are that teachers, curriculum developers, and textbook writers, if they are to minimize potential misconceptions, need to be cognizant of the relationship between physics and chemistry teaching, of the need to test for erroneous preconceptions about current before teaching about electrochemical (galvanic) and electrolytic cells, and of the difficulties experienced by students when using more than one model to explain scientific phenomena.

  17. The chemistry of O in reduction processes of the GaAs native oxides

    NASA Astrophysics Data System (ADS)

    Cuberes, M. T.; Sacedon, J. L.

    1992-05-01

    We present an X-ray photoelectron spectroscopy (XPS) study of the interfacial chemical reactions during the total reduction of a 5 Å thick GaAs native oxide layer accomplished in two separate stages. First, the As2O3 has been selectively reduced by annealing the oxidized surface at increasing temperatures. In the second stage, the reduction of the Ga oxides has been completed at room temperature by Si deposition. The total amount of O at the GaAs interface remains constant during both processes. During the As2O3 thermal reduction, the analysis of the Ga2p{3}/{2} and Ga LMM spectra shows that, depending on the annealing temperature, GaOx (x < {3}/{2}) or Ga2O3 growth occurs. The Si promoted of the Ga oxides results in the formation of Si oxides of different stoichiometry at the GaAs surface.

  18. A facile approach to prepare graphene via solvothermal reduction of graphite oxide

    SciTech Connect

    Yuan, Bihe; Bao, Chenlu; Qian, Xiaodong; Wen, Panyue; Xing, Weiyi; Song, Lei; Hu, Yuan

    2014-07-01

    Highlights: • Graphene was prepared via a novel and facile solvothermal reduction method for graphite oxide. • Most of the oxygen functional groups of graphite oxide were removed. • The reduced graphene oxide obtained was featured with bilayer nanosheets. - Abstract: In this work, a facile reduction strategy is reported for the fabrication of graphene. Graphite oxide (GO) is reduced via a novel solvothermal reaction in a mixed solution of acetone and sodium hypochlorite (NaClO). The structure, surface chemistry, morphology and thermal stability of the as-prepared reduced graphene oxide (RGO) are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results indicate that most of the oxygenated groups in GO are effectively removed in this solvothermal reaction. The novel reduction method provides a simple, cost-effective and efficient strategy for the fabrication of graphene.

  19. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. 1998 annual progress report

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1998-06-01

    'Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting their ability to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine the authors quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction and FeRB activity. This report summarizes research accomplished after approximately 1.5 yr of a 3-yr project. A central hypothesis of the research is that advective elimination of the primary end-product of Fe(III) oxide reduction, Fe(II), will enhance the rate and extent of microbial Fe(III) oxide reduction in open experimental systems. This hypothesis is based on previous studies in the laboratory which demonstrated that association of evolved Fe(II) with oxide and FeRB cell surfaces (via adsorption or surface precipitation) is a primary cause for cessation of Fe(III) oxide reduction activity in batch culture experiments. Semicontinuous culturing was adopted as a first approach to test this basic hypothesis. Synthetic goethite or natural Fe(III) oxide-rich subsoils were used as Fe(III) sources, with the Fe(III)-reducing bacterium Shewanella alga as the test organism.'

  20. Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

    NASA Technical Reports Server (NTRS)

    Mukhopadhyay, C. K.; Fox, P. L.

    1998-01-01

    Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

  1. Reduction study of oxidized two-dimensional graphene-based materials by chemical and thermal reduction methods

    NASA Astrophysics Data System (ADS)

    Douglas, Amber M.

    Graphene is a two-dimensional (2D) sp2-hybridized carbon-based material possessing properties which include high electrical conductivity, ballistic thermal conductivity, tensile strength exceeding that of steel, high flexural strength, optical transparency, and the ability to adsorb and desorb atoms and molecules. Due to the characteristics of said material, graphene is a candidate for applications in integrated circuits, electrochromic devices, transparent conducting electrodes, desalination, solar cells, thermal management materials, polymer nanocomposites, and biosensors. Despite the above mentioned properties and possible applications, very few technologies have been commercialized utilizing graphene due to the high cost associated with the production of graphene. Therefore, a great deal of effort and research has been performed to produce a material that provides similar properties, reduced graphene oxide due (RGO) to the ease of commercial scaling of the production processes. This material is typically prepared through the oxidation of graphite in an aqueous media to graphene oxide (GO) followed by reduction to yield RGO. Although this material has been extensively studied, there is a lack of consistency in the scientific community regarding the analysis of the resulting RGO material. In this dissertation, a study of the reduction methods for GO and an alternate 2D carbon-based material, humic acid (HA), followed by analysis of the materials using Raman spectroscopy and Energy Dispersive X-ray Spectroscopy (EDS). Means of reduction will include chemical and thermal methods. Characterization of the material has been carried out on both before and after reduction.

  2. Comparative survey of potential nitrate and sulfate reduction rates in aquatic sediments

    NASA Astrophysics Data System (ADS)

    Laverman, Anniet M.; Pallud, Céline; Abell, Jeffrey; Cappellen, Philippe Van

    2012-01-01

    Nitrate and sulfate are two major terminal electron acceptors of anaerobic respiration in nearshore sediments. Potential nitrate and sulfate reduction rates (NRR and SRR) were determined on surficial sediments sampled at 14 sites representing a wide range of shallow-water depositional environments. The rates were obtained by supplying undisturbed slices of sediments with nitrate, sulfate or both using a flow-through reactor technique. No external electron donor was added to the sediments. The results indicate that all studied sediments harbored viable and coexisting nitrate- and sulfate-reducing communities, which were able to instantaneously consume the electron acceptors supplied to the reactors. On average, NRR exceeded SRR by about one order of magnitude (309 ± 180 nmol NO3- cm-3 h-1versus 37 ± 29 nmol SO42- cm-3 h-1). The NRR:SRR molar ratio, however, varied significantly from site to site, with values ranging from 1.7 to 59. Nitrite production, indicative of incomplete nitrate reduction, was observed in all studied sediments and, on average, accounted for 45% of NRR (range 3-80%). Production of sulfate under nitrate-reducing conditions was observed in 10 out of 14 of the studied sediments, suggesting a common occurrence of sulfide oxidation coupled to nitrate reduction. Oxidation of sulfide accounted for 0 to 40% of NRR in the nitrate-only experiments. When both electron acceptors were supplied simultaneously, net sulfate consumption decreased on average by 45%. The effect of nitrate on SRR was highly variable, however, ranging from near complete inhibition to a 25% enhancement of SRR. Overall, the results of this study point to the need to critically reassess the model formulations used to represent anaerobic respiration processes and their interactions in early diagenetic models.

  3. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

    PubMed

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-11-15

    This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate. PMID:27434736

  4. Pilot-scale equipment development for pyrochemical reduction of spent oxide fuel

    SciTech Connect

    Herrmann, S.D.; King, R.W.; Durstine, K.R.; Eberl, C.S.

    1998-07-01

    Argonne National Laboratory (ANL) has developed and is presently demonstrating the electrometallurgical conditioning of sodium-bonded spent metal fuel from Experimental Breeder Reactor II, resulting in uranium, ceramic, and metal waste forms. Equipment is being developed at ANL which will precondition irradiated oxide fuel and demonstrate the application of electrometallurgical conditioning to such non-metallic fuels as well. The oxide reduction process preconditions irradiated oxide fuel such that uranium and transuranic (TRU) constituents are chemically reduced into metallic form via a molten Li/LiCl-based reduction system. In this form the spent fuel is further conditioned in an electrorefiner and waste handling equipment, thereby placing the uranium, TRU elements, and fissions products into stable forms suitable for placement in a long-term repository. Development of the Li/LiCl-based oxide reduction process has proceeded at lab- (nominally 50 grams of heavy metal (HM)) and engineering-scale (nominally 10-kg of HM) for unirradiated oxide fuel. The presentation described the process and equipment design for scale-up from lab- and engineering-scale reduction of unirradiated oxide fuel in gloveboxes to pilot-scale (up to 100-kg of HM) reduction of irradiated oxide fuel in a hot cell. [Abstract only.

  5. Physics of the solid-phase oxidation and reduction of metals

    NASA Astrophysics Data System (ADS)

    Roshchin, V. E.; Roshchin, A. V.

    2015-05-01

    The transfer of electric charges and mass in the crystal lattice of an oxide is analyzed. The massand electrotransport in oxides are shown to be caused by ionic displacements; to be interrelated; and to occur via scattering of charged ionic vacancies, which form at the surface of contact of oxide with a reducing or oxidizing medium. A general physical model is developed to describe metal reduction and oxidation. This model is based on the universal principle of equality of the number of elementary charge carriers, namely, electrons and protons, in any phase and the contingency of mass- and electrotransport in an ionic crystal lattice.

  6. Determination of carbon by the oxidation reduction reaction with chromium

    NASA Technical Reports Server (NTRS)

    Mashkovich, L.; Kuteynikov, A. F.

    1978-01-01

    Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

  7. Nitrate reduction by denitrifying anaerobic methane oxidizing microorganisms can reach a practically useful rate.

    PubMed

    Cai, Chen; Hu, Shihu; Guo, Jianhua; Shi, Ying; Xie, Guo-Jun; Yuan, Zhiguo

    2015-12-15

    Methane in biogas has been proposed to be an electron donor to facilitate complete nitrogen removal using denitrifying anaerobic methane oxidizing (DAMO) microorganisms in an anaerobic ammonium oxidation (anammox) reactor, by reducing the nitrate produced. However, the slow growth and the low activity of DAMO microorganisms cast a serious doubt about the practical usefulness of such a process. In this study, a previously established lab-scale membrane biofilm reactor (MBfR), with biofilms consisting of a coculture of DAMO and anammox microorganisms, was operated to answer if the DAMO reactor can achieve a nitrate reduction rate that can potentially be applied for wastewater treatment. Through progressively increasing nitrate and ammonium loading rates to the reactor, a nitrate removal rate of 684 ± 10 mg-N L(-1) d(-1) was achieved after 453 days of operation. This rate is, to our knowledge, by far the highest reported for DAMO reactors, and far exceeds what is predicted to be required for nitrate removal in a sidestream (5.6-135 mg-N L(-1) d(-1)) or mainstream anammox reactor (3.2-124 mg-N L(-1) d(-1)). Mass balance analysis showed that the nitrite produced by nitrate reduction was jointly reduced by anammox bacteria at a rate of 354 ± 3 mg-N L(-1) d(-1), accompanied by an ammonium removal rate of 268 ± 2 mg-N L(-1) d(-1), and DAMO bacteria at a rate of 330 ± 9 mg-N L(-1) d(-1). This study shows that the nitrate reduction rate achieved by the DAMO process can be high enough for removing nitrate produced by anammox process, which would enable complete nitrogen removal from wastewater. PMID:26414889

  8. Oxidation versus reductive detoxification of SO sub 2 by chloroplasts

    SciTech Connect

    Ghisi, R.; Dittrich, A.P.M.; Heber, U. )

    1990-03-01

    Intact chloroplasts isolated from spinach (Spinacia oleracea L. cv Yates) both oxidized and reduced added sulfite in the light. Oxidation was fast only when endogenous superoxide dismutase was inhibited by cyanide. It was largely suppressed by scavengers of oxygen radicals. After addition of O-acetylserine, chloroplasts reduced sulfite to cysteine and exhibited sulfite-dependent oxygen evolution. Cysteine synthesis from sulfite was faster than from sulfate. The results are discussed in relation to species-specific differences in the phytotoxicity of SO{sub 2}.

  9. Method for catalyzing oxidation/reduction reactions of simple molecules

    SciTech Connect

    Bicker, D.; Bonaventura, J.

    1988-06-14

    A method for oxidizing carbon monoxide to carbon dioxide is described comprising: (1) contacting, together, carbon monoxide, a nitrogen-containing chelating agent and water; wherein the chelating agent is at least one member selected from the group consisting of methmeoglobin bound to a support, ferric hemoglobin bound to a support, iron-containing porphyrins bound to a support, and sperm whale myoglobin bound to a support, wherein the support is glass, a natural fiber, a synthetic fiber, a gel, charcoal, carbon ceramic material, a metal oxide, a synthetic polymer, a zeolite, a silica compound of an alumina compound; and (2) obtaining carbon dioxide.

  10. Nitric oxide reductions in a multi-zone reheat furnace

    SciTech Connect

    Harder, R.F. )

    1994-04-01

    A reduced excess air combustion control technique was developed for an existing 3-zone reheat furnace that would reduce NO[sub x] emissions to conform with regulatory air quality requirements. The results indicate that reduced excess air combustion controls can be utilized for obtaining NO[sub x] reductions in a multi-zone steel reheat furnace. This study provides support for considering this control strategy as a possible first step toward reheat furnace NO[sub x] control. For new furnace installations, low NO[sub x] burners combined with other technologies provide the greatest benefit. However, for existing furnaces, a control system retrofit may be the most cost-effective short range option. Regarding actual NO[sub x] reduction costs after installation and testing were complete, this control methodology cost approximately $8,500/ton NO[sub x] reduction.

  11. Process for the reduction of nitrogen oxides in an effluent using a heterocyclic hydrocarbon

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.

    1989-12-19

    This patent describes a process for the reduction of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprises injecting a treatment agent which comprises furfural into the effluent under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

  12. Process for the reduction of nitrogen oxides in an effluent using a hydroxy amino hydrocarbon

    SciTech Connect

    Sullivan, J.C.; Epperly, W.R.

    1989-02-07

    A process is described for the reduction of the concentration of nitrogen oxide in an effluent from the combustion of a carbonaceous fuel, the process comprising injecting a treatment agent comprising a hydroxy amino hydrocarbon into an effluent at an effluent temperature of greater than about 1300/sup 0/F under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

  13. DEVELOPMENT AND EVALUATION OF A MATHEMATICAL MODEL FOR THE TRANSPORT AND OXIDATION-REDUCTION OF COEDTA

    EPA Science Inventory

    Oxidation-reduction reactions, catalyzed by iron and manganese oxides, influence the subsurface mobility of a variety of toxic metals. In the work reported here, we develop a new model for the transport of the redox-sensitive CoEDTA complex, and we test the model against publishe...

  14. Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

    SciTech Connect

    Thornton, Edward C.; Baolin Deng; Jurisson, Silvia Sabine; Terry, Jeff

    2006-06-01

    The mobility of many contaminants is redox sensitive and thus related to the reduction oxidation characteristics of the environment. Immobilization of certain contaminants (e.g., chromium, uranium, and technetium) can be achieved by reducing the contaminant. One remediation approach to achieving this is the application of diluted hydrogen sulfide gas mixtures, which may have particular value in vadose zone applications. Previous work has shown this approach to be viable for Cr(VI) remediation of soil waste sites. The primary objective of the current research is to assess the potential of in situ gaseous treatment to the immobilization of U(VI) and Tc(VII). This work also addresses basic science aspects of understanding the redox-related aspects of the mobility of these contaminants in the natural environment, thus providing a mechanistic-based understanding needed to successfully achieve remediation.

  15. Early Steps of Pore Formation During Stainless Steel Oxides Reduction with Hydrogen at 1373 K (1100 °C)

    NASA Astrophysics Data System (ADS)

    Badin, Valentin; Diamanti, Entela; Forêt, Pierre; Darque-Ceretti, Evelyne

    2016-04-01

    A 10- µm-thick oxide scale covering an austenitic stainless steel has been reduced with hydrogen at 1373 K (1100 °C) to study the resulting porosity. Multiple methods of characterization have been employed on samples with the reduction time ranging from 5 seconds to 30 minutes. Focus has been placed on short durations to highlight the different steps occurring during the reduction. Three main steps have been observed, leading to micrometer scale porosity. The process is regarded as a potential new method for creating metal porous surfaces.

  16. Effects of Adiponectin Including Reduction of Androstenedione Secretion and Ovarian Oxidative Stress Parameters In Vivo

    PubMed Central

    Comim, Fabio V.; Gutierrez, Karina; Bridi, Alessandra; Bochi, Guilherme; Chemeris, Raisa; Rigo, Melânia L.; Dau, Andressa Minussi P.; Cezar, Alfredo S.; Moresco, Rafael Noal; Gonçalves, Paulo Bayard Dias

    2016-01-01

    Adiponectin is the most abundantly produced human adipokine with anti-inflammatory, anti-oxidative, and insulin-sensitizing properties. Evidence from in vitro studies has indicated that adiponectin has a potential role in reproduction because it reduces the production of androstenedione in bovine theca cells in vitro. However, this effect on androgen production has not yet been observed in vivo. The current study evaluated the effect of adiponectin on androstenedione secretion and oxidative stress parameters in a rodent model. Seven-week-old female Balb/c mice (n = 33), previously treated with equine gonadotropin chorionic, were assigned to one of four different treatments: Group 1, control (phosphate-buffered saline); Group 2, adiponectin 0.1 μg/mL; Group 3, adiponectin 1.0 μg/mL; Group 4, adiponectin 5.0 μg/mL. After 24 h, all animals were euthanized and androstenedione levels were measured in the serum while oxidative stress markers were quantified in whole ovary tissue. Female mice treated with adiponectin exhibited a significant reduction (about 60%) in serum androstenedione levels in comparison to controls. Androstenedione levels decreased from 0.78 ± 0.4 ng/mL (mean ± SD) in controls to 0.28 ± 0.06 ng/mL after adiponectin (5 μg/mL) treatment (P = 0.01). This change in androgen secretion after 24 hours of treatment was associated with a significant reduction in the expression of CYP11A1 and STAR (but not CYP17A1). In addition, ovarian AOPP product levels, a direct product of protein oxidation, decreased significantly in adiponectin-treated mice (5 μg/mL); AOPP (mean ± SD) decreased to 4.3 ± 2.1 μmol/L in comparison with that of the controls (11.5 ± 1.7 μmol/L; P = 0.0003). Our results demonstrated for the first time that acute treatment with adiponectin reduced the levels of a direct oxidative stress marker in the ovary as well as decreased androstenedione serum levels in vivo after 24 h. PMID:27158926

  17. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    SciTech Connect

    Gopalan, Srikanth

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  18. Thermodynamic Analysis and Reduction of Bismuth Oxide by Ethanol

    NASA Astrophysics Data System (ADS)

    Korkmaz, Fatih; Cetinkaya, Senol; Eroglu, Serafettin

    2016-05-01

    In this study, ethanol (C2H5OH) was used as an alternative reducing agent for Bi2O3 because ethanol is renewable, increasingly available, and low in toxicity. Thermodynamic analysis was performed to predict experimental conditions for Bi formation in the Bi2O3-C2H5OH-Ar system at Ar/C2H5OH molar ratio of 10.5. Ar was used as a carrier gas for ethanol. Bi2O3 reduction kinetics was investigated at 600 K to 800 K (327 °C to 527 °C) at Ar flow rate 85 sccm. Ar flow rate was also varied at 600 K and 800 K (327 °C and 527 °C) in order to clarify the mechanism controlling the process. Mass measurements and XRD analyses were carried out to determine the extent of reduction. Fractional conversion increased with time and temperature. Full reduction time decreased from ~180 minutes at 600 K (327 °C) to ~30 minutes at 700 K and 800 K (427 °C and 527 °C). The reduction process was external mass transfer limited (Q a = 7.2 kJ/mole) above 700 K (427 °C). It was controlled by intrinsic chemical kinetics (Q a = 54.7 kJ/mole) below 700 K (427 °C). In the mass-transport-controlled regime, the extent of reduction increased with flow rate as predicted by a mass-transport theory. Possible reaction pathways were discussed using the thermodynamic and experimental results.

  19. Thermodynamic Analysis and Reduction of Bismuth Oxide by Ethanol

    NASA Astrophysics Data System (ADS)

    Korkmaz, Fatih; Cetinkaya, Senol; Eroglu, Serafettin

    2016-08-01

    In this study, ethanol (C2H5OH) was used as an alternative reducing agent for Bi2O3 because ethanol is renewable, increasingly available, and low in toxicity. Thermodynamic analysis was performed to predict experimental conditions for Bi formation in the Bi2O3-C2H5OH-Ar system at Ar/C2H5OH molar ratio of 10.5. Ar was used as a carrier gas for ethanol. Bi2O3 reduction kinetics was investigated at 600 K to 800 K (327 °C to 527 °C) at Ar flow rate 85 sccm. Ar flow rate was also varied at 600 K and 800 K (327 °C and 527 °C) in order to clarify the mechanism controlling the process. Mass measurements and XRD analyses were carried out to determine the extent of reduction. Fractional conversion increased with time and temperature. Full reduction time decreased from ~180 minutes at 600 K (327 °C) to ~30 minutes at 700 K and 800 K (427 °C and 527 °C). The reduction process was external mass transfer limited ( Q a = 7.2 kJ/mole) above 700 K (427 °C). It was controlled by intrinsic chemical kinetics ( Q a = 54.7 kJ/mole) below 700 K (427 °C). In the mass-transport-controlled regime, the extent of reduction increased with flow rate as predicted by a mass-transport theory. Possible reaction pathways were discussed using the thermodynamic and experimental results.

  20. Elevated acetate concentrations in the rhizosphere of Spartina alterniflora and potential influences on sulfate reduction

    NASA Technical Reports Server (NTRS)

    Hines, Mark E.; Tugel, Joyce B.; Giblin, A. E.; Banta, G. T.; Hobbie, J. E.

    1992-01-01

    Acetate is important in anaerobic metabolism of non-vegetated sediments but its role in salt marsh soils was not investigated thoroughly. Acetate concentrations, oxidation (C-14) and SO4(2-) reduction (S-35) were measured in S. alterniflora soils in NH and MA. Pore water from cores contained greater than 0.1 mM acetate and in some instances greater than 1.0 mM. Non-destructive samples contained less than 0.01 mM. Acetate was associated with roots and concentrations were highest during vegetative growth and varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of SO4(2-) reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a significant percentage of SO4(2-) reduction. These results differ markedly from data for non-vegetated coastal sediments where acetate levels are low, oxidation rate constants are high and acetate oxidation rates greatly exceed rates of SO4(2-) reduction. The discrepancy between rates of acetate oxidation and SO4(2-) reduction in marsh soils may be due either to the utilization of substrates other than acetate by SO4(2-) reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria.

  1. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

    NASA Astrophysics Data System (ADS)

    Verdaguer-Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E. L.; Chorkendorff, Ib; Dahl, Søren

    2012-12-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction is severely poisoned. Poisoning at the cathode explains the majority of the losses observed in polymer electrolyte membrane fuel cells contaminated with ammonia. Voltammetry in deaerated solution suggest that the poisoning can be attributed to either ammonium oxidation or increased binding to OH species.

  2. Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source.

    PubMed

    Timmers, Peer Ha; Suarez-Zuluaga, Diego A; van Rossem, Minke; Diender, Martijn; Stams, Alfons Jm; Plugge, Caroline M

    2016-06-01

    The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with (13)C-labeled CH4 ((13)CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, (13)C-labeled CO2 ((13)CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with (13)CO2 production and no methanogenesis occurred, excluding TMO as a possible source for (13)CO2 production from (13)CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment. PMID:26636551

  3. In Vitro Enzymatic Reduction Kinetics of Mineral Oxides by Membrane Fractions from Shewanella oneidensis MR-1

    SciTech Connect

    Ruebush,S.; Icopini, G.; Brantley, S.; Tien, M.

    2006-01-01

    This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite

  4. In vitro enzymatic reduction kinetics of mineral oxides by membrane fractions from Shewanella oneidensis MR-1

    NASA Astrophysics Data System (ADS)

    Ruebush, Shane S.; Icopini, Gary A.; Brantley, Susan L.; Tien, Ming

    2006-01-01

    This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite

  5. Potential of solar cooling systems for peak demand reduction

    SciTech Connect

    Pesaran, A A; Neymark, J

    1994-11-01

    We investigated the technical feasibility of solar cooling for peak demand reduction using a building energy simulation program (DOE2.1D). The system studied was an absorption cooling system with a thermal coefficient of performance of 0.8 driven by a solar collector system with an efficiency of 50% with no thermal storage. The analysis for three different climates showed that, on the day with peak cooling load, about 17% of the peak load could be met satisfactorily with the solar-assisted cooling system without any thermal storage. A performance availability analysis indicated that the solar cooling system should be designed for lower amounts of available solar resources that coincide with the hours during which peak demand reduction is required. The analysis indicated that in dry climates, direct-normal concentrating collectors work well for solar cooling; however, in humid climates, collectors that absorb diffuse radiation work better.

  6. Crystallographic studies of V44 mutants of Clostridium pasteurianum rubredoxin: Effects of side-chain size on reduction potential

    SciTech Connect

    Park, Il Yeong; Eidsness, Marly K.; Lin, I-Jin; Gebel, Erika B.; Youn, Buhyun; Harley, Jill L.; Machonkin, Timothy E.; Frederick, Ronnie O.; Markley, John L.; Smith, Eugene T.; Ichiye, Toshiko; Kang, ChulHee

    2010-11-16

    Understanding the structural origins of differences in reduction potentials is crucial to understanding how various electron transfer proteins modulate their reduction potentials and how they evolve for diverse functional roles. Here, the high-resolution structures of several Clostridium pasteurianum rubredoxin (Cp Rd) variants with changes in the vicinity of the redox site are reported in order to increase this understanding. Our crystal structures of [V44L] (at 1.8 {angstrom} resolution), [V44A] (1.6 {angstrom}), [V44G] (2.0 {angstrom}) and [V44A, G45P] (1.5 {angstrom}) Rd (all in their oxidized states) show that there is a gradual decrease in the distance between Fe and the amide nitrogen of residue 44 upon reduction in the size of the side chain of residue 44; the decrease occurs from leucine to valine, alanine or glycine and is accompanied by a gradual increase in their reduction potentials. Mutation of Cp Rd at position 44 also changes the hydrogen-bond distance between the amide nitrogen of residue 44 and the sulfur of cysteine 42 in a size-dependent manner. Our results suggest that residue 44 is an important determinant of Rd reduction potential in a manner dictated by side-chain size. Along with the electric dipole moment of the 43-44 peptide bond and the 44-42 NHS type hydrogen bond, a modulation mechanism for solvent accessibility through residue 41 might regulate the redox reaction of the Rds. Proteins 2004.

  7. New potential of the reductive alkylation of amines

    NASA Astrophysics Data System (ADS)

    Gusak, K. N.; Ignatovich, Zh V.; Koroleva, E. V.

    2015-03-01

    Available data on the reductive alkylation of amines with carbonyl compounds — a key method for the preparation of secondary and tertiary amines — are described systematically. The review provides information on the relevant reducing agents and catalysts and on the use of chiral catalysts in stereo- and enantiocontrolled reactions of amine synthesis. The effect of the reactant and catalyst structures on the reaction rates and chemo- and stereo(enantio)selectivity is considered. The bibliography includes 156 references.

  8. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment.

    PubMed

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Meyer, Rikke Louise; Revsbech, Niels Peter; Schramm, Andreas; Nielsen, Lars Peter; Risgaard-Petersen, Nils

    2014-08-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4-6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

  9. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

    PubMed Central

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

    2014-01-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

  10. Process for the reduction of nitrogen oxides in an effluent

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.

    1988-09-13

    A process is described for reducing the concentration of nitrogen oxides in an effluent from the combustion of a carbonaceous fuel, which process comprises injecting into the effluent ammonia and an enhancer selected from the group consisting of hexamethylenetetramine, a lower carbon alcohol, a hydroxyl amino hydrocarbon, sugar, furfural, furfural derivatives, an amino acid, a protein-containing composition, mixtures of ortho-, meta-, and para-methyl phenols, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, calcium cyanamide, biuret, 1,1'-azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, and mixtures thereof, at an effluent temperature above about 1300/sup 0/F and a molar ratio of nitrogen in the ammonia and enhancer to the baseline nitrogen oxides level of about 1:5 to about 6:1 wherein the excess of oxygen in the effluent is no greater than about 6%.

  11. Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

    USGS Publications Warehouse

    Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

    1995-01-01

    Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

  12. Methylmercury Oxidative Degradation Potentials in Contaminated and Pristine Sediments of the Carson River, Nevada

    PubMed Central

    Oremland, R. S.; Miller, L. G.; Dowdle, P.; Connell, T.; Barkay, T.

    1995-01-01

    Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [(sup14)C]MeHg was detected at all sites as indicated by the formation of (sup14)CO(inf2) and (sup14)CH(inf4). Oxidative demethylation was indicated by the formation of (sup14)CO(inf2) and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., (sup14)CO(inf2)/(sup14)CH(inf4) ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of (sup14)CO(inf2) was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and (sup14)CO(inf2) accounted for 98% of the product formed from [(sup14)C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of (sup14)CO(inf2) from [(sup14)C]MeHg, while 2-bromoethanesulfonic acid blocked production of (sup14)CH(inf4). These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments. PMID:16535081

  13. Thermogravimetric study of the reduction of oxides of nickel and chromium

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.

    1973-01-01

    The controlled hydrogen, carbon, and hydrogen-carbon reductions of the oxides of nickel and chromium were evaluated by thermogravimetric means. The materials studied were nickel (nickelous) oxide (NiO) and chromic sesquioxide (Cr2O3), mixed NiO-Cr2O3, and oxidized nickel - 20-percent chromium (Ni-20Cr). NiO was effectively reduced by all three atmospheres, Cr2O3 only by hydrogen-carbon, NiO-Cr2O3 by hydrogen and hydrogen-carbon, and oxidized Ni-20Cr by hydrogen and hydrogen-carbon and to a considerable extent by carbon alone. The results suggest that the presence of nickel promotes the reduction of Cr2O3. However, no definite explanation could be reached for the effectiveness of the hydrogen-carbon reduction of Cr2O3.

  14. Use of Carnosine for Oxidative Stress Reduction in Different Pathologies

    PubMed Central

    Prokopieva, V. D.; Yarygina, E. G.; Bokhan, N. A.; Ivanova, S. A.

    2016-01-01

    The main properties and biological effects of the antioxidant carnosine, the natural dipeptide β-alanyl-L-histidine, are considered. Data on the effective use of carnosine in different pathologies are presented. Special attention is paid to issues of use of carnosine in neurologic and mental diseases, in alcoholism as well as in physiological states accompanied by activation of free-radical processes and formation of oxidative stress. PMID:26904160

  15. Use of Carnosine for Oxidative Stress Reduction in Different Pathologies.

    PubMed

    Prokopieva, V D; Yarygina, E G; Bokhan, N A; Ivanova, S A

    2016-01-01

    The main properties and biological effects of the antioxidant carnosine, the natural dipeptide β-alanyl-L-histidine, are considered. Data on the effective use of carnosine in different pathologies are presented. Special attention is paid to issues of use of carnosine in neurologic and mental diseases, in alcoholism as well as in physiological states accompanied by activation of free-radical processes and formation of oxidative stress. PMID:26904160

  16. Ferric iron reduction by sulfur- and iron-oxidizing bacteria.

    PubMed Central

    Brock, T D; Gustafson, J

    1976-01-01

    Acidophilic bacteria of the genera Thiobacillus and Sulfolobus are able to reduce ferric iron when growing on elemental sulfur as an energy source. It has been previously thought that ferric iron serves as a nonbiological oxidant in the formation of acid mine drainage and in the leaching of ores, but these results suggest that bacterial catalysis may play a significant role in the reactivity of ferric iron. PMID:825043

  17. A theoretical framework for predicting the oxidative stress potential of oxide nanoparticles.

    PubMed

    Burello, Enrico; Worth, Andrew P

    2011-06-01

    In this paper we propose a theoretical model that predicts the oxidative stress potential of oxide nanoparticles by looking at the ability of these materials to perturb the intracellular redox state. The model uses reactivity descriptors to build the energy band structure of oxide nanoparticles, assuming a particle diameter larger than 20-30 nm and no surface states in the band gap, and predicts their ability to induce an oxidative stress by comparing the redox potentials of relevant intracellular reactions with the oxides' energy structure. Nanoparticles displaying band energy values comparable with redox potentials of antioxidants or radical formation reactions have the ability to cause an oxidative stress and a cytotoxic response in vitro. We discuss the model's predictions for six relevant oxide nanoparticles (TiO(2), CuO, ZnO, FeO, Fe(2)O(3), Fe(3)O(4)) with literature in vitro studies and calculate the energy structure for 64 additional oxide nanomaterials. Such a framework would guide the development of more rational and efficient screening strategies avoiding random or exhaustive testing of new nanomaterials. PMID:21609138

  18. Corannulene reduction. Spectroscopic detection of all anionic oxidation states

    SciTech Connect

    Baumgarten, M.; Gherghel, L.; Wagner, M.; Weitz, A.; Rabinovitz, M. |; Cheng, P.C.; Scott, L.T.

    1995-06-14

    The reduction of corannulene (1) has been followed by parallel detection of optical absorption, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) spectroscopies. The major findings are the existence of a diamagnetic dianion that can be observed in NMR and negligible counterion influences in the mono- and dianion. The diamagnetic state of the dianion is also supported by vanishing EPR intensity and semiempirical calculations and exhibits one indistinguishable proton NMR resonance at -5.6 ppm for potassium and lithium as counterions, respectively. The NMR signal is strongly temperature dependent and can only be obtained at low temperature (T < 230 K) where the line width decreases with temperature. Further reduction to the trianion and tetraanion succeeds with Li as the reducing metal, but not with K even at ambient temperatures. The EPR spectra of the trianion show a pronounced temperature dependence with at least two Li cations being strongly coupled. 18 refs., 3 figs., 3 tabs.

  19. The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts

    SciTech Connect

    Digby Macdonald

    2005-04-15

    The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

  20. Transition Metal Oxide Alloys as Potential Solar Energy Conversion Materials

    SciTech Connect

    Toroker, Maytal; Carter, Emily A.

    2013-02-21

    First-row transition metal oxides (TMOs) are inexpensive potentia alternative materials for solar energy conversion devices. However, some TMOs, such as manganese(II) oxide, have band gaps that are too large for efficiently absorbing solar energy. Other TMOs, such as iron(II) oxide, have conduction and valence band edges with the same orbital character that may lead to unfavorably high electron–hole recombination rates. Another limitation of iron(II) oxide is that the calculated valence band edge is not positioned well for oxidizing water. We predict that key properties, including band gaps, band edge positions, and possibly electron–hole recombination rates, may be improved by alloying TMOs that have different band alignments. A new metric, the band gap center offset, is introduced for simple screening of potential parent materials. The concept is illustrated by calculating the electronic structure of binary oxide alloys that contain manganese, nickel, iron, zinc, and/or magnesium, within density functional theory (DFT)+U and hybrid DFT theories. We conclude that alloys of iron(II) oxide are worth evaluating further as solar energy conversion materials.

  1. Hydrogen and Formate Oxidation Coupled to Dissimilatory Reduction of Iron or Manganese by Alteromonas putrefaciens

    PubMed Central

    Lovley, Derek R.; Phillips, Elizabeth J. P.; Lonergan, Debra 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. PMID:16347876

  2. 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.

  3. Current concepts in the pathophysiology of fibromyalgia: the potential role of oxidative stress and nitric oxide.

    PubMed

    Ozgocmen, Salih; Ozyurt, Huseyin; Sogut, Sadik; Akyol, Omer

    2006-05-01

    Fibromyalgia (FM) is a common chronic pain syndrome with an unknown etiology. Recent years added new information to our understanding of FM pathophysiology. Researches on genetics, biogenic amines, neurotransmitters, hypothalamic-pituitary-adrenal axis hormones, oxidative stress, and mechanisms of pain modulation, central sensitization, and autonomic functions in FM revealed various abnormalities indicating that multiple factors and mechanisms are involved in the pathogenesis of FM. Oxidative stress and nitric oxide may play an important role in FM pathophysiology, however it is still not clear whether oxidative stress abnormalities documented in FM are the cause or the effect. This should encourage further researches evaluating the potential role of oxidative stress and nitric oxide in the pathophysiology of FM and the efficacy of antioxidant treatments (omega-3 and -6 fatty acids, vitamins and others) in double blind and placebo controlled trials. These future researches will enhance our understanding of the complex pathophysiology of this disorder. PMID:16328420

  4. 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

  5. Modulation of potassium channel function by methionine oxidation and reduction

    PubMed Central

    Ciorba, Matthew A.; Heinemann, Stefan H.; Weissbach, Herbert; Brot, Nathan; Hoshi, Toshinori

    1997-01-01

    Oxidation of amino acid residues in proteins can be caused by a variety of oxidizing agents normally produced by cells. The oxidation of methionine in proteins to methionine sulfoxide is implicated in aging as well as in pathological conditions, and it is a reversible reaction mediated by a ubiquitous enzyme, peptide methionine sulfoxide reductase. The reversibility of methionine oxidation suggests that it could act as a cellular regulatory mechanism although no such in vivo activity has been demonstrated. We show here that oxidation of a methionine residue in a voltage-dependent potassium channel modulates its inactivation. When this methionine residue is oxidized to methionine sulfoxide, the inactivation is disrupted, and it is reversed by coexpression with peptide methionine sulfoxide reductase. The results suggest that oxidation and reduction of methionine could play a dynamic role in the cellular signal transduction process in a variety of systems. PMID:9275229

  6. Microbial Fe(III) Oxide Reduction in Chocolate Pots Hot Springs, Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Fortney, N. W.; Roden, E. E.; Boyd, E. S.; Converse, B. J.

    2014-12-01

    Previous work on dissimilatory iron reduction (DIR) in Yellowstone National Park (YNP) has focused on high temperature, low pH environments where soluble Fe(III) is utilized as an electron acceptor for respiration. Much less attention has been paid to DIR in lower temperature, circumneutral pH environments, where solid phase Fe(III) oxides are the dominant forms of Fe(III). This study explored the potential for DIR in the warm (ca. 40-50°C), circumneutral pH Chocolate Pots hot springs (CP) in YNP. Most probable number (MPN) enumerations and enrichment culture studies confirmed the presence of endogenous microbial communities that reduced native CP Fe(III) oxides. Enrichment cultures demonstrated sustained DIR coupled to acetate and lactate oxidation through repeated transfers over ca. 450 days. Pyrosequencing of 16S rRNA genes indicated that the dominant organisms in the enrichments were closely affiliated with the well known Fe(III) reducer Geobacter metallireducens. Additional taxa included relatives of sulfate reducing bacterial genera Desulfohalobium and Thermodesulfovibrio; however, amendment of enrichments with molybdate, an inhibitor of sulfate reduction, suggested that sulfate reduction was not a primary metabolic pathway involved in DIR in the cultures. A metagenomic analysis of enrichment cultures is underway in anticipation of identifying genes involved in DIR in the less well-characterized dominant organisms. Current studies are aimed at interrogating the in situ microbial community at CP. Core samples were collected along the flow path (Fig. 1) and subdivided into 1 cm depth intervals for geochemical and microbiological analysis. The presence of significant quantities of Fe(II) in the solids indicated that DIR is active in situ. A parallel study investigated in vitro microbial DIR in sediments collected from three of the coring sites. DNA was extracted from samples from both studies for 16S rRNA gene and metagenomic sequencing in order to obtain a

  7. Galvanic interpretation of self-potential signals associated withmicrobial sulfate-reduction

    SciTech Connect

    Williams, Kenneth H.; Hubbard, Susan S.; Banfield, Jillian F.

    2007-05-02

    We have evaluated the usefulness of the self-potential (SP)geophysical method to track the onset and location of microbialsulfate-reduction in saturated sediments during organic carbon amendment.Following stimulation of sulfate-reducing bacteria (SRB) by addition oflactate, anomalous voltages exceeding 600 mV correlated in space and timewith the accumulation of dissolved sulfide. Abiotic experiments in whichthe sulfide concentration at the measurement electrode was systematicallyvaried showed a positive correlation between the magnitude of the SPanomaly and differences in the half-cell potential associated with themeasurement and reference electrodes. Thus, we infer that the SPanomaliesresulted from electrochemical differences that developedbetween sulfide-rich regions and areas having higher oxidation potential.In neither experiment did generation of an SP anomaly require thepresence of an in situ electronic conductor, as is required by othermodels. These findings emphasize the importance of incorporation ofelectrochemical effects at electrode surfaces in interpretation of SPdata from geophysical studies. We conclude that SP measurements provide aminimally invasive means for monitoring stimulated sulfate-reductionwithin saturated sediments.

  8. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella oneidensis MR-1

    SciTech Connect

    Shi, Liang; Rosso, Kevin M.; Clarke, Thomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, Jim K.

    2012-02-15

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved the machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III) oxidation have not been identified, they are believed to relay the electrons in the periplasm to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can

  9. Characterization of methionine oxidation and methionine sulfoxide reduction using methionine-rich cysteine-free proteins

    PubMed Central

    2012-01-01

    Background Methionine (Met) residues in proteins can be readily oxidized by reactive oxygen species to Met sulfoxide (MetO). MetO is a promising physiological marker of oxidative stress and its inefficient repair by MetO reductases (Msrs) has been linked to neurodegeneration and aging. Conventional methods of assaying MetO formation and reduction rely on chromatographic or mass spectrometry procedures, but the use of Met-rich proteins (MRPs) may offer a more streamlined alternative. Results We carried out a computational search of completely sequenced genomes for MRPs deficient in cysteine (Cys) residues and identified several proteins containing 20% or more Met residues. We used these MRPs to examine Met oxidation and MetO reduction by in-gel shift assays and immunoblot assays with antibodies generated against various oxidized MRPs. The oxidation of Cys-free MRPs by hydrogen peroxide could be conveniently monitored by SDS-PAGE and was specific for Met, as evidenced by quantitative reduction of these proteins with Msrs in DTT- and thioredoxin-dependent assays. We found that hypochlorite was especially efficient in oxidizing MRPs. Finally, we further developed a procedure wherein antibodies made against oxidized MRPs were isolated on affinity resins containing same or other oxidized or reduced MRPs. This procedure yielded reagents specific for MetO in these proteins, but proved to be ineffective in developing antibodies with broad MetO specificity. Conclusion Our data show that MRPs provide a convenient tool for characterization of Met oxidation, MetO reduction and Msr activities, and could be used for various aspects of redox biology involving reversible Met oxidation. PMID:23088625

  10. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis.

    PubMed

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela C; Calle-Vallejo, Federico; Nørskov, Jens K; Jaramillo, Thomas F; Rossmeisl, Jan

    2012-10-28

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn(2)O(3) and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V and 1.0 V, a potential region between the ORR and the OER relevant conditions. Next, we perform density function theory (DFT) calculations to understand the changes in the MnO(x) surface as a function of potential and to elucidate reaction mechanisms that lead to high activities observed in the experiments. Using DFT, we construct surface Pourbaix and free energy diagrams of three different MnO(x) surfaces and identify 1/2 ML HO* covered Mn(2)O(3) and O* covered MnO(2), as the active surfaces for the ORR and the OER, respectively. Additionally, we find that the ORR occurs through an associative mechanism and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis and experimental methods offers an understanding of manganese oxide oxygen electrocatalysis at the atomic level, achieving fundamental insight that can potentially be

  11. Sulfonamide antibiotic reduction in aquatic environment by application of fenton oxidation process

    PubMed Central

    2013-01-01

    Presence of antibiotics in the environment may cause potential risk for aquatic environment and organisms. In this research, Fenton oxidation process was offered as an effective method for removal of antibiotic sulfamethoxazole from aqueous solutions. The experiments were performed on laboratory-scale study under complete mixing at 25±2°C. The effects of initial antibiotic concentration, molar ratio of H2O2/Fe+2, solution pH, concentration of H2O2, Fe+2 and reaction time was studied on the oxidation of sulfamethoxazole in three level. The results indicated that the optimal parameters for Fenton process were as follows: molar ratio of [H2O2]/[Fe+2] = 1.5, pH= 4.5, and contact time= 15 min. In this situation, the antibiotic removal and COD reduction were achieved 99.99% and 64.7-70.67%, respectively. Although, Fenton reaction could effectively degrade antibiotic sulfamethoxazole under optimum experimental conditions, however, the rate of mineralization was not completed. This process can be considered to eliminate other refractory antibiotics with similar structure or to increase their biodegradability. PMID:23570238

  12. Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation.

    PubMed

    Thomas, J Mathew; Hernandez, Rafael; Kuo, Chiang-Hai

    2008-06-30

    Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NACs contaminated waters. The process consists of the combination of zero-valent iron and an ozonation based treatment technique. Corrosion promoters are added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluene (DNT) was treated with the integrated process using a recirculated batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhances the reduction of 2,4-DNT with zero-valent iron. The addition of corrosion promoters resulted in 62% decrease in 2,4-DNT concentration to 2,4-diaminotoluene. The data shows that iron reduced the 2,4-DNT and ozone oxidized these products resulting in a 73% removal of TOC and a 96% decrease in 2,4-DNT concentration. PMID:18166266

  13. Geochemical control of microbial Fe(III) reduction potential in wetlands: Comparison of the rhizosphere to non-rhizosphere soil

    USGS Publications Warehouse

    Weiss, J.V.; Emerson, D.; Megonigal, J.P.

    2004-01-01

    We compared the reactivity and microbial reduction potential of Fe(III) minerals in the rhizosphere and non-rhizosphere soil to test the hypothesis that rapid Fe(III) reduction rates in wetland soils are explained by rhizosphere processes. The rhizosphere was defined as the area immediately adjacent to a root encrusted with Fe(III)-oxides or Fe plaque, and non-rhizosphere soil was 0.5 cm from the root surface. The rhizosphere had a significantly higher percentage of poorly crystalline Fe (66??7%) than non-rhizosphere soil (23??7%); conversely, non-rhizosphere soil had a significantly higher proportion of crystalline Fe (50??7%) than the rhizosphere (18??7%, P<0.05 in all cases). The percentage of poorly crystalline Fe(III) was significantly correlated with the percentage of FeRB (r=0.76), reflecting the fact that poorly crystalline Fe(III) minerals are labile with respect to microbial reduction. Abiotic reductive dissolution consumed about 75% of the rhizosphere Fe(III)-oxide pool in 4 h compared to 23% of the soil Fe(III)-oxide pool. Similarly, microbial reduction consumed 75-80% of the rhizosphere pool in 10 days compared to 30-40% of the non-rhizosphere soil pool. Differences between the two pools persisted when samples were amended with an electron-shuttling compound (AQDS), an Fe(III)-reducing bacterium (Geobacter metallireducens), and organic carbon. Thus, Fe(III)-oxide mineralogy contributed strongly to differences in the Fe(III) reduction potential of the two pools. Higher amounts of poorly crystalline Fe(III) and possibly humic substances, and a higher Fe(III) reduction potential in the rhizosphere compared to the non-rhizosphere soil, suggested the rhizosphere is a site of unusually active microbial Fe cycling. The results were consistent with previous speculation that rapid Fe cycling in wetlands is due to the activity of wetland plant roots. ?? 2004 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

  14. Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

    NASA Astrophysics Data System (ADS)

    Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

    2013-03-01

    A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

  15. Osthole improves alcohol-induced fatty liver in mice by reduction of hepatic oxidative stress.

    PubMed

    Zhang, Jianjun; Xue, Jie; Wang, Hengbin; Zhang, Yan; Xie, Meilin

    2011-05-01

    The aim of our study was to examine the therapeutic effect of osthole, an active constituent isolated from the fruit of Cnidium monnieri (L.) Cusson, on alcohol-induced fatty liver in mice and investigate its potential mechanisms of treatment. A mouse alcoholic fatty liver model was established by feeding 52% alcohol for 4 weeks. These experimental mice were then treated with osthole 10, 20 and 40 mg/kg for 6 weeks. The levels of serum total cholesterol (TC), triglyceride (TG), low density lipoprotein-cholesterol (LDL-C) and hepatic tissue contents of TC, TG and malondialdehyde (MDA) in osthole-treated groups were significantly decreased, while the level of superoxide dismutase (SOD) was significantly increased compared with the model group. Moreover, the cytochrome P450 (CYP) 2E1 and diacylglycerol acyltransferase (DGAT) mRNA expressions in mouse liver were significantly decreased, and the carnitine palmitoyltransferase (CPT) 1A mRNA expression was increased by osthole treatment. Importantly, the histological evaluation of liver demonstrated that osthole dramatically decreased lipid accumulation. It was concluded that osthole was effective in treating mouse alcoholic fatty liver, and its main mechanisms might be related to reduction of hepatic oxidative stress, including the inhibition of reactive oxygen species (ROS) production, enhancement of antioxidative enzyme activity, and reduction of lipid accumulation and peroxidation. PMID:20981870

  16. Remote fabrication and irradiation test of recycled nuclear fuel prepared by the oxidation and reduction of spent oxide fuel

    NASA Astrophysics Data System (ADS)

    Jin Ryu, Ho; Chan Song, Kee; Il Park, Geun; Won Lee, Jung; Seung Yang, Myung

    2005-02-01

    A direct dry recycling process was developed in order to reuse spent pressurized light water reactor (LWR) nuclear fuel in CANDU reactors without the separation of sensitive nuclear materials such as plutonium. The benefits of the dry recycling process are the saving of uranium resources and the reduction of spent fuel accumulation as well as a higher proliferation resistance. In the process of direct dry recycling, fuel pellets separated from spent LWR fuel rods are oxidized from UO2 to U3O8 at 500 °C in an air atmosphere and reduced into UO2 at 700 °C in a hydrogen atmosphere, which is called OREOX (oxidation and reduction of oxide fuel). The pellets are pulverized during the oxidation and reduction processes due to the phase transformation between cubic UO2 and orthorhombic U3O8. Using the oxide powder prepared from the OREOX process, the compaction and sintering processes are performed in a remote manner in a shielded hot cell due to the high radioactivity of the spent fuel. Most of the fission gas and volatile fission products are removed during the OREOX and sintering processes. The mini-elements fabricated by the direct dry recycling process are irradiated in the HANARO research reactor for the performance evaluation of the recycled fuel pellets. Post-irradiation examination of the irradiated fuel showed that microstructural evolution and fission gas release behavior of the dry-recycled fuel were similar to high burnup UO2 fuel.

  17. Reduction of iron-oxide-carbon composites: part I. Estimation of the rate constants

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  18. Potential for Sonic Boom Reduction of the Boeing HSCT

    NASA Technical Reports Server (NTRS)

    Haglund, George T.

    1999-01-01

    The HSR sonic boom technology program includes a goal of reducing the objectionable aspects of sonic boom. Earlier HSCT sonic boom studies considered achieving significant sonic boom reduction by the use of arrow-wing planforms and detailed shaping of the airplane to produce shaped waveforms (non N-waves) at the ground. While these design efforts were largely successful, the added risk and cost of the airplanes were judged to be unacceptable. The objective of the current work is to explore smaller configuration refinements that could lead to reduced sonic boom impact, within design and operational constraints. A somewhat modest target of 10% reduction in sonic boom maximum overpressure was selected to minimize the effect on the configuration performance. This work was a joint NASA/Industry effort, utilizing the respective strengths of team members at Boeing, NASA Langley, and NASA Ames. The approach used was to first explore a wide range of modifications and airplane characteristics for their effects on sonic boom and drag, using classical Modified Linear Theory (MLT) methods. CFD methods were then used to verify promising, modifications and to analyze modifications for which the MLT methods were not appropriate. The tea m produced a list of configuration changes with their effects on sonic boom and, in some cases, an estimate of the drag penalty. The most promising modifications were applied to produce a boom-softened derivative of the baseline Boeing High Speed Civil Transport (HSCT) configuration. This boom-softened configuration was analyzed in detail for the reduce sonic boom impact and also for the effect of the configuration modifications on drag, weight, and overall performance relative to the baseline.

  19. Potential for microbial oxidation of ferrous iron in basaltic glass.

    PubMed

    Xiong, Mai Yia; Shelobolina, Evgenya S; Roden, Eric E

    2015-05-01

    Basaltic glass (BG) is an amorphous ferrous iron [Fe(II)]-containing material present in basaltic rocks, which are abundant on rocky planets such as Earth and Mars. Previous research has suggested that Fe(II) in BG can serve as an energy source for chemolithotrophic microbial metabolism, which has important ramifications for potential past and present microbial life on Mars. However, to date there has been no direct demonstration of microbially catalyzed oxidation of Fe(II) in BG. In this study, three different culture systems were used to investigate the potential for microbial oxidation of Fe(II) in BG, including (1) the chemolithoautotrophic Fe(II)-oxidizing, nitrate-reducing "Straub culture"; (2) the mixotrophic Fe(II)-oxidizing, nitrate-reducing organism Desulfitobacterium frappieri strain G2; and (3) indigenous microorganisms from a streambed Fe seep in Wisconsin. The BG employed consisted of clay and silt-sized particles of freshly quenched lava from the TEB flow in Kilauea, Hawaii. Soluble Fe(II) or chemically reduced NAu-2 smectite (RS) were employed as positive controls to verify Fe(II) oxidation activity in the culture systems. All three systems demonstrated oxidation of soluble Fe(II) and/or structural Fe(II) in RS, whereas no oxidation of Fe(II) in BG material was observed. The inability of the Straub culture to oxidize Fe(II) in BG was particularly surprising, as this culture can oxidize other insoluble Fe(II)-bearing minerals such as biotite, magnetite, and siderite. Although the reason for the resistance of the BG toward enzymatic oxidation remains unknown, it seems possible that the absence of distinct crystal faces or edge sites in the amorphous glass renders the material resistant to such attack. These findings have implications with regard to the idea that Fe(II)-Si-rich phases in basalt rocks could provide a basis for chemolithotrophic microbial life on Mars, specifically in neutral-pH environments where acid-promoted mineral dissolution and

  20. DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS

    SciTech Connect

    Dr. Ates Akyurtlu; Dr. Jale F. Akyurtlu

    2001-05-31

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long-term stability and durability of the prepared sorbent/catalysts. In the first year of the project, the catalysts were investigated by the temperature-programmed reduction (TPR) technique. The results from TPR indicated that the interaction with support appears to promote reduction at lower temperatures

  1. Thermogravimetric, Calorimetric, and Structural Studies of the Co3 O4 /CoO Oxidation/Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Unruh, Karl; Cichocki, Ronald; Kelly, Brian; Poirier, Gerald

    2015-03-01

    To better assess the potential of cobalt oxide for thermal energy storage (TES), the Co3O4/CoO oxidation/reduction reaction has been studied by thermogravimetric (TGA), calorimetric (DSC), and x-ray diffraction (XRD) measurements in N2 and atmospheric air environments. TGA measurements showed an abrupt mass loss of about 6.6% in both N2 and air, consistent with the stoichiometric reduction of Co3O4 to CoO and structural measurements. The onset temperature of the reduction of Co3O4 in air was only weakly dependent on the sample heating rate and occurred at about 910 °C. The onset temperature for the oxidation of CoO varied between about 850 and 875 °C for cooling rates between 1 and 20 °C/min, but complete re-conversion to Co3O4 could only be achieved at the slowest cooling rates. Due to the dependence of the rate constant on the oxygen partial pressure, the oxidation of Co3O4 in a N2 environment occurred at temperatures between about 775 and 825 °C for heating rates between 1 and 20 °C/min and no subsequent re-oxidation of the reduced Co3O4 was observed on cooling to room temperature. In conjunction with a measured transition heat of about 600 J/g of Co3O4, these measurements indicate that cobalt oxide is a viable TES material.

  2. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  3. Ferrous iron removal promotes microbial reduction of crystalline iron(III) oxides

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1999-06-01

    Semicontinuous cultures were used to assess the effect of aqueous Fe(II) removal on the dissimilatory reduction of crystalline Fe(III) oxides by Shewanella alga strain BrY. Aqueous phase replacement in semicontinuous cultures resulted in a 2--3-fold increase in the cumulative amount of Fe(II) produced from synthetic goethite reduction over a 2-month incubation period, compared to parallel batch cultures. A more modest (maximum 30%) but significant stimulation of natural subsoil Fe(III) oxide reduction was observed. The extended Fe(III) reduction resulted from enhanced generation of aqueous Fe(II) which was periodically removed from the cultures. A concomitant stimulation of bacterial protein production was detected, which suggested that Fe(II) removal also promoted bacterial growth. A simulation model in which Fe(II) sorption to the solid-phase resulted in blockage of surface reduction sites captured the contrasting behavior of the batch vs semicontinuous Gt reduction systems. The findings indicate that elimination of Fe(II) via advective transport could play a significant role in governing the rate and extent of microbial Fe(III) oxide reduction in sedimentary environments.

  4. Potential Reduction of Interstitial Myocardial Fibrosis With Renal Denervation

    PubMed Central

    Doltra, Adelina; Messroghli, Daniel; Stawowy, Philipp; Hassel, Jan‐Hendrik; Gebker, Rolf; Leppänen, Olli; Gräfe, Michael; Schneeweis, Christopher; Schnackenburg, Bernhard; Fleck, Eckart; Kelle, Sebastian

    2014-01-01

    Background Hypertensive cardiomyopathy is characterized by myocyte hypertrophy and interstitial fibrosis. The effects of renal denervation (RD) on the heart are poorly understood. New magnetic resonance imaging techniques (extracellular volume fraction) permit the quantitative assessment of myocardial fibrosis. Our aim was to study the effects of RD on myocardial fibrosis. Methods and Results Twenty‐three patients with resistant hypertension undergoing RD and 5 resistant hypertensive controls were prospectively included. Cardiac magnetic resonance imaging at 1.5 T was performed before RD and at 6‐month follow‐up. Indexed left ventricular mass, septal extracellular volume fraction, and indexed absolute extracellular volume (a quantitative measure of extracellular matrix) were quantified. All data are reported as mean±SD deviation (median). Decreases in systolic (161.96±19.09 [160] versus 144.78±16.48 [143] mm Hg, P<0.0001) and diastolic (85.61±12.88 [83] versus 80.39±11.93 [81] mm Hg, P=0.018) blood pressures and in indexed left ventricular mass (41.83±10.20 [41.59] versus 37.72±7.44 [38.49] g/m1.7, P=0.001) were observed at follow‐up only in RD patients. No significant differences in extracellular volume were found (26.24±3.92% [26.06%] versus 25.74±4.53% [25.63%], P=0.605). A significant decrease in absolute extracellular volume was observed after 6 months in RD patients exclusively (10.36±2.25 [10.79] versus 9.25±2.38 [9.79] mL/m1.7, P=0.031). This effect was observed independently of blood pressure reduction. Conclusions RD significantly decreases left ventricular mass, while extracellular volume remains stable. Our results suggest that the observed left ventricular mass decrease was due not exclusively to a reversion of myocyte hypertrophy but also to an additional reduction in collagen content, indicating interstitial myocardial fibrosis. PMID:25516438

  5. Ionization potentials of transparent conductive indium tin oxide films covered with a single layer of fluorine-doped tin oxide nanoparticles grown by spray pyrolysis deposition

    SciTech Connect

    Fukano, Tatsuo; Motohiro, Tomoyoshi; Ida, Takashi; Hashizume, Hiroo

    2005-04-15

    Indium tin oxide (ITO) films deposited with single layers of monodispersive fluorine-doped tin oxide (FTO) nanoparticles of several nanometers in size were grown on glass substrates by intermittent spray pyrolysis deposition using conventional atomizers. These films have significantly higher ionization potentials than the bare ITO and FTO films grown using the same technique. The ITO films covered with FTO particles of 7 nm in average size show an ionization potential of 5.01 eV, as compared with {approx}4.76 and {approx}4.64 eV in ITO and FTO films, respectively, which decreases as the FTO particle size increases. The ionization potentials are practically invariant against oxidation and reduction treatments, promising a wide application of the films to transparent conducting oxide electrodes in organic electroluminescent devices and light-emitting devices of high efficiencies.

  6. Ionization potentials of transparent conductive indium tin oxide films covered with a single layer of fluorine-doped tin oxide nanoparticles grown by spray pyrolysis deposition

    NASA Astrophysics Data System (ADS)

    Fukano, Tatsuo; Motohiro, Tomoyoshi; Ida, Takashi; Hashizume, Hiroo

    2005-04-01

    Indium tin oxide (ITO) films deposited with single layers of monodispersive fluorine-doped tin oxide (FTO) nanoparticles of several nanometers in size were grown on glass substrates by intermittent spray pyrolysis deposition using conventional atomizers. These films have significantly higher ionization potentials than the bare ITO and FTO films grown using the same technique. The ITO films covered with FTO particles of 7nm in average size show an ionization potential of 5.01eV, as compared with ˜4.76 and ˜4.64eV in ITO and FTO films, respectively, which decreases as the FTO particle size increases. The ionization potentials are practically invariant against oxidation and reduction treatments, promising a wide application of the films to transparent conducting oxide electrodes in organic electroluminescent devices and light-emitting devices of high efficiencies.

  7. Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants.

    PubMed

    Senior, Constance L

    2006-01-01

    A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. PMID:16499143

  8. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Fritz B.; Lee, Wonyoung

    2015-11-01

    We report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte-electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  9. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    SciTech Connect

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  10. Jet Noise Reduction Potential from Emerging Variable Cycle Technologies

    NASA Technical Reports Server (NTRS)

    Henderson, Brenda; Bridges, James; Wernet, Mark

    2012-01-01

    Acoustic and flow-field experiments were conducted on exhaust concepts for the next generation supersonic, commercial aircraft. The concepts were developed by Lockheed Martin (LM), Rolls-Royce Liberty Works (RRLW), and General Electric Global Research (GEGR) as part of an N+2 (next generation forward) aircraft system study initiated by the Supersonics Project in NASA s Fundamental Aeronautics Program. The experiments were conducted in the Aero-Acoustic Propulsion Laboratory at the NASA Glenn Research Center. The exhaust concepts utilized ejectors, inverted velocity profiles, and fluidic shields. One of the ejector concepts was found to produce stagnant flow within the ejector and the other ejector concept produced discrete-frequency tones that degraded the acoustic performance of the model. The concept incorporating an inverted velocity profile and fluid shield produced overall-sound-pressure-level reductions of 6 dB relative to a single stream nozzle at the peak jet noise angle for some nozzle pressure ratios. Flow separations in the nozzle degraded the acoustic performance of the inverted velocity profile model at low nozzle pressure ratios.

  11. Quantifying food losses and the potential for reduction in Switzerland.

    PubMed

    Beretta, Claudio; Stoessel, Franziska; Baier, Urs; Hellweg, Stefanie

    2013-03-01

    A key element in making our food systems more efficient is the reduction of food losses across the entire food value chain. Nevertheless, food losses are often neglected. This paper quantifies food losses in Switzerland at the various stages of the food value chain (agricultural production, postharvest handling and trade, processing, food service industry, retail, and households), identifies hotspots and analyses the reasons for losses. Twenty-two food categories are modelled separately in a mass and energy flow analysis, based on data from 31 companies within the food value chain, and from public institutions, associations, and from the literature. The energy balance shows that 48% of the total calories produced (edible crop yields at harvest time and animal products, including slaughter waste) is lost across the whole food value chain. Half of these losses would be avoidable given appropriate mitigation measures. Most avoidable food losses occur at the household, processing, and agricultural production stage of the food value chain. Households are responsible for almost half of the total avoidable losses (in terms of calorific content). PMID:23270687

  12. Jet Noise Reduction Potential From Emerging Variable Cycle Technologies

    NASA Technical Reports Server (NTRS)

    2012-01-01

    Acoustic and flow-field experiments were conducted on exhaust concepts for the next generation supersonic, commercial aircraft. The concepts were developed by Lockheed Martin (LM), Rolls-Royce Liberty Works (RRLW), and General Electric Global Research (GEGR) as part of an N+2 (next generation forward) aircraft system study initiated by the Supersonics Project in NASA s Fundamental Aeronautics Program. The experiments were conducted in the Aero-Acoustic Propulsion Laboratory at the NASA Glenn Research Center. The exhaust concepts utilized ejectors, inverted velocity profiles, and fluidic shields. One of the ejector concepts was found to produce stagnant flow within the ejector and the other ejector concept produced discrete-frequency tones that degraded the acoustic performance of the model. The concept incorporating an inverted velocity profile and fluid shield produced overall-sound-pressure-level reductions of 6 dB relative to a single stream nozzle at the peak jet noise angle for some nozzle pressure ratios. Flow separations in the nozzle degraded the acoustic performance of the inverted velocity profile model at low nozzle pressure ratios.

  13. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface

    NASA Astrophysics Data System (ADS)

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-01

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  14. Electron transfer of Pseudomonas aeruginosa CP1 in electrochemical reduction of nitric oxide.

    PubMed

    Zhou, Shaofeng; Huang, Shaobin; He, Jiaxin; Li, Han; Zhang, Yongqing

    2016-10-01

    This study reports catalytic electro-chemical reduction of nitric oxide (NO) enhanced by Pseudomonas aeruginosa strain CP1. The current generated in the presence of bacteria was 4.36times that in the absence of the bacteria. The strain was able to catalyze electro-chemical reduction of NO via indirect electron transfer with an electrode, revealed by a series of cyclic voltammetry experiments. Soluble electron shuttles secreted into solution by live bacteria were responsible for the catalytic effects. The enhancement of NO reduction was also confirmed by detection of nitrous oxide; the level of this intermediate was 46.4% higher in the presence of bacteria than in controls, illustrated that the electron transfer pathway did not directly reduce nitric oxide to N2. The findings of this study may offer a new model for bioelectrochemical research in the field of NO removal by biocatalysts. PMID:27426634

  15. Reduction of a phosphorus oxide and acid reaction set

    SciTech Connect

    Twarowski, A.

    1995-07-01

    It has been predicted for some time that hypersonic aircraft will suffer from diminished fuel efficiency due to the slow speed of radical recombination in the nozzle of the aircraft and the consequent expulsion of high-energy fragments during high Mach number flight. The addition of small amounts of phosphine combustion products (phosphorus oxides and acids) to water vapor has been found to result in a faster relaxation rate of OH to its equilibrium density following H{sub 2}O photolysis. This article describes the systematic construction of a reaction model of 162 phosphorus reactions among 17 phosphorus-containing species. Those reactions that contribute to the reestablishment of equilibrium following the perturbation of the system by H{sub 2}O photolysis or by an increase in temperature are identified. A thermodynamic free energy function is used to quantify the rate of system relaxation back to equilibrium for a series of 36 reaction conditions covering a temperature range of 1,500 to 3,000 K, a gas density range of 5 {times} 10{sup {minus}7} to 5 {times} 10{sup {minus}5} mol/cm{sup 3} and a fuel equivalence ratio of 0.8 to 1.2.

  16. Direct Reduction of Ferrous Oxides to form an Iron-Rich Alternative Charge Material

    NASA Astrophysics Data System (ADS)

    Ünal, H. İbrahim; Turgut, Enes; Atapek, Ş. H.; Alkan, Attila

    2015-12-01

    In this study, production of sponge iron by direct reduction of oxides and the effect of reductant on metallization were investigated. In the first stage of the study, scale formed during hot rolling of slabs was reduced in a rotating furnace using solid and gas reductants. Coal was used as solid reductant and hydrogen released from the combustion reaction of LNG was used as the gas one. The sponge iron produced by direct reduction was melted and solidified. In the second stage, Hematite ore in the form of pellets was reduced using solid carbon in a furnace heated up to 1,100°C for 60 and 120 minutes. Reduction degree of process was evaluated as a function of time and the ratio of Cfix/Fetotal. In the third stage, final products were examined using scanning electron microscope and microanalysis was carried out by energy dispersive x-ray spectrometer attached to the electron microscope. It is concluded that (i) direct reduction using both solid and gas reductants caused higher metallization compared to using only solid reductant, (ii) as the reduction time and ratio of Cfix/Fetotal increased %-reduction of ore increased.

  17. Localized conductive patterning via focused electron beam reduction of graphene oxide

    NASA Astrophysics Data System (ADS)

    Kim, Songkil; Kulkarni, Dhaval D.; Henry, Mathias; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V.; Fedorov, Andrei G.

    2015-03-01

    We report on a method for "direct-write" conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

  18. Localized conductive patterning via focused electron beam reduction of graphene oxide

    SciTech Connect

    Kim, Songkil; Henry, Mathias; Kulkarni, Dhaval D.; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V.; Fedorov, Andrei G.

    2015-03-30

    We report on a method for “direct-write” conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

  19. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    DOEpatents

    Pence, Dallas T.; Thomas, Thomas R.

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  20. Process for the reduction of nitrogen oxides in an effluent using sugar

    SciTech Connect

    Epperly, W R.; Sullivan, J.C.

    1989-10-31

    This patent describes a process for the reduction of the concentration of nitrogen oxides in the oxygen-rich effluent from the combustion of a carbonaceous fuel. The process comprising injecting a treatment agent which comprises urea and sugar into an effluent having a temperature of greater than about 1300 {degrees} F. under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

  1. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore

    PubMed Central

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-01-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process. PMID:27374991

  2. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore.

    PubMed

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-01-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process. PMID:27374991

  3. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore

    NASA Astrophysics Data System (ADS)

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-07-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C) subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process.

  4. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  5. Evidence of alloy formation during reduction of platinized tin oxide surfaces

    NASA Technical Reports Server (NTRS)

    Gardner, Steven D.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

    1989-01-01

    Ion scattering spectroscopy, Auger electron spectroscopy, and electron spectroscopy for chemical analysis have been used to examine a platinized tin oxide catalyst surface before, during, and after reduction by annealing under vacuum at 250 to 450 C. These techniques were then used to examine the reduced surface after a room-temperature, low-pressure oxygen exposure. The spectral results and the behavior of the reduced surface toward oxygen exposure both indicate that a Pt/Sn alloy is produced during reduction.

  6. Reduction and structural evolution of graphene oxide sheets under hydrothermal treatment

    NASA Astrophysics Data System (ADS)

    Niu, Yongan; Fang, Qinghong; Zhang, Xin; Zhang, Panpan; Li, Yao

    2016-09-01

    This work carefully investigated the hydrothermal reduction of graphene oxide (GO) sheets. To evaluate the reduced extent, the as-prepared GO and RGO sheets in different conditions were measured by FT-IR, UV-Vis, Raman spectra and TEM morphologies. It revealed that the hydrothermal reduction of GO sheets was undergone four steps and the optimal condition was treated at 180 °C for 24 h. These RGO sheets exhibited the expectant morphologies and maintained the original sizes.

  7. Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis

    SciTech Connect

    Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E; Lin, Wenbin

    2011-07-22

    Catalytically competent Ir, Re, and Ru complexes H2L1–H2L6 with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr6O4(OH)4(bpdc)6 (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L1–L6 ligands allowed the construction of highly crystalline UiO-67 frameworks (metal–organic frameworks (MOFs) 1–6) that were doped with L1–L6 ligands. MOFs 1–6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m2/g. MOFs 1–6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1–3 containing [Cp*IrIII(dcppy)Cl] (H2L1), [Cp*IrIII(dcbpy)Cl]Cl (H2L2), and [IrIII(dcppy)2(H2O)2]OTf (H2L3) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h–1. The [ReI(CO)3(dcbpy)Cl] (H2L4) derivatized MOF 4 served as an active catalyst for photocatalytic CO2 reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H2L4. MOFs 5 and 6 contained phosphorescent [IrIII(ppy)2(dcbpy)]Cl (H2L5) and [RuII(bpy)2(dcbpy)]Cl2 (H2L6) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO2 reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic

  8. Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma

    NASA Astrophysics Data System (ADS)

    Vesel, Alenka; Mozetic, Miran; Balat-Pichelin, Marianne

    2016-11-01

    Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.

  9. Mechanism of Cr(VI) reduction by Aspergillus niger: enzymatic characteristic, oxidative stress response, and reduction product.

    PubMed

    Gu, Yanling; Xu, Weihua; Liu, Yunguo; Zeng, Guangming; Huang, Jinhui; Tan, Xiaofei; Jian, Hao; Hu, Xi; Li, Fei; Wang, Dafei

    2015-04-01

    Bioremediation of hexavalent chromium by Aspergillus niger was attributed to the reduction product (trivalent chromium) that could be removed in precipitation and immobilized inside the fungal cells and on the surface of mycelium. The site location of reduction was conducted with assays of the permeabilized cells, cell-free extracts, and cell debris, which confirmed that the chromate reductase was mainly located in the soluble fraction of cells. The oxidation-reduction process was accompanied by the increase of reactive oxygen species and antioxidant levels after hexavalent chromium treatment. Michaelis-Menten constant (K(m)) and maximum reaction rate (V(max)), obtained from the Lineweaver-Burk plot were 14.68 μM and 434 μM min(-1) mg(-1) of protein, respectively. Scanning electron microscopy and Raman spectra analyses manifested that both Cr(VI) and Cr(III) species were present on the mycelium. Fourier transform-infrared spectroscopy analysis suggested that carboxyl, hydroxide, amine, amide, cyano-group, and phosphate groups from the fungal cell wall were involved in chromium binding by the complexation with the Cr(III) and Cr(VI) species. A Cr(VI) removal mechanism of Cr(VI) reduction followed by the surface immobilization and intracellular accumulation of Cr(III) in living A. niger was present. PMID:25408081

  10. LC-MS/MS analysis and comparison of oxidative damages on peptides induced by pathogen reduction technologies for platelets.

    PubMed

    Prudent, Michel; Sonego, Giona; Abonnenc, Mélanie; Tissot, Jean-Daniel; Lion, Niels

    2014-04-01

    Pathogen reduction technologies (PRT) are photochemical processes that use a combination of photosensitizers and UV-light to inactivate pathogens in platelet concentrates (PCs), a blood-derived product used to prevent hemorrhage. However, different studies have questioned the impact of PRT on platelet function and transfusion efficacy, and several proteomic analyses revealed possible oxidative damages to proteins. The present work focused on the oxidative damages produced by the two main PRT on peptides. Model peptides containing residues prone to oxidation (tyrosine, histidine, tryptophane, and cysteine) were irradiated with a combination of amotosalen/UVA (Intercept process) or riboflavin/UVB (Mirasol-like process). Modifications were identified and quantified by liquid chromatography coupled to tandem mass spectrometry. Cysteine-containing peptides formed disulfide bridges (R-SS-R, -2 Da; favored following amotosalen/UVA), sulfenic and sulfonic acids (R-SOH, +16 Da, R-SO3H, +48 Da, favored following riboflavin/UVB) upon treatment and the other amino acids exhibited different oxidations revealed by mass shifts from +4 to +34 Da involving different mechanisms; no photoadducts were detected. These amino acids were not equally affected by the PRT and the combination riboflavin/UVB generated more oxidation than amotosalen/UVA. This work identifies the different types and sites of peptide oxidations under the photochemical treatments and demonstrates that the two PRT may behave differently. The potential impact on proteins and platelet functions may thus be PRT-dependent. PMID:24470194

  11. LC-MS/MS Analysis and Comparison of Oxidative Damages on Peptides Induced by Pathogen Reduction Technologies for Platelets

    NASA Astrophysics Data System (ADS)

    Prudent, Michel; Sonego, Giona; Abonnenc, Mélanie; Tissot, Jean-Daniel; Lion, Niels

    2014-04-01

    Pathogen reduction technologies (PRT) are photochemical processes that use a combination of photosensitizers and UV-light to inactivate pathogens in platelet concentrates (PCs), a blood-derived product used to prevent hemorrhage. However, different studies have questioned the impact of PRT on platelet function and transfusion efficacy, and several proteomic analyses revealed possible oxidative damages to proteins. The present work focused on the oxidative damages produced by the two main PRT on peptides. Model peptides containing residues prone to oxidation (tyrosine, histidine, tryptophane, and cysteine) were irradiated with a combination of amotosalen/UVA (Intercept process) or riboflavin/UVB (Mirasol-like process). Modifications were identified and quantified by liquid chromatography coupled to tandem mass spectrometry. Cysteine-containing peptides formed disulfide bridges (R-SS-R, -2 Da; favored following amotosalen/UVA), sulfenic and sulfonic acids (R-SOH, +16 Da, R-SO3H, +48 Da, favored following riboflavin/UVB) upon treatment and the other amino acids exhibited different oxidations revealed by mass shifts from +4 to +34 Da involving different mechanisms; no photoadducts were detected. These amino acids were not equally affected by the PRT and the combination riboflavin/UVB generated more oxidation than amotosalen/UVA. This work identifies the different types and sites of peptide oxidations under the photochemical treatments and demonstrates that the two PRT may behave differently. The potential impact on proteins and platelet functions may thus be PRT-dependent.

  12. Potential CO2 Emission Reduction by Development of Non-Grain-Based Bioethanol in China

    NASA Astrophysics Data System (ADS)

    Li, Hongqiang; Wang, Limao; Shen, Lei

    2010-10-01

    Assessment of the potential CO2 emission reduction by development of non-grain-based ethanol in China is valuable for both setting up countermeasures against climate change and formulating bioethanol policies. Based on the land occupation property, feedstock classification and selection are conducted, identifying sweet sorghum, cassava, and sweet potato as plantation feedstocks cultivated from low-quality arable marginal land resources and molasses and agricultural straws as nonplantation feedstocks derived from agricultural by-products. The feedstock utilization degree, CO2 reduction coefficient of bioethanol, and assessment model of CO2 emission reduction potential of bioethanol are proposed and established to assess the potential CO2 emission reduction by development of non-grain-based bioethanol. The results show that China can obtain emission reduction potentials of 10.947 and 49.027 Mt CO2 with non-grain-based bioethanol in 2015 and 2030, which are much higher than the present capacity, calculated as 1.95 Mt. It is found that nonplantation feedstock can produce more bioethanol so as to obtain a higher potential than plantation feedstock in both 2015 and 2030. Another finding is that developing non-grain-based bioethanol can make only a limited contribution to China’s greenhouse gas emission reduction. Moreover, this study reveals that the regions with low and very low potentials for emission reduction will dominate the spatial distribution in 2015, and regions with high and very high potentials will be the majority in 2030.

  13. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.

    PubMed

    Maiyalagan, Thandavarayan; Jarvis, Karalee A; Therese, Soosairaj; Ferreira, Paulo J; Manthiram, Arumugam

    2014-01-01

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co(3+/4+):3d energy with the top of the O(2-):2p band. PMID:24862287

  14. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj; Ferreira, Paulo J.; Manthiram, Arumugam

    2014-05-01

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co3+/4+:3d energy with the top of the O2-:2p band.

  15. Biocatalysis mechanism for p-fluoronitrobenzene degradation in the thermophilic bioelectrocatalysis system: Sequential combination of reduction and oxidation.

    PubMed

    Wang, Yanfeng; Zhang, Xueqin; Feng, Huajun; Liang, Yuxiang; Shen, Dongsheng; Long, Yuyang; Zhou, Yuyang; Dai, Qizhou

    2016-09-01

    To verify the potentially synthetic anodic and cathodic biocatalysis mechanism in bioelectrocatalysis systems (BECSs), a single-chamber thermophilic bioelectrocatalysis system (R3) was operated under strictly anaerobic conditions using the biocathode donated dual-chamber (R1) and bioanode donated dual-chamber (R2) BECSs as controls. Direct bioelectrocatalytic oxidation was found to be infeasible while bioelectrocatalytic reduction was the dominant process for p-Fluoronitrobenzene (p-FNB) removal, with p-FNB removal of 0.188 mM d(-1) in R1 and 0.182 mM d(-1) in R3. Cyclic voltammetry experiments confirmed that defluorination in the BECSs was an oxidative metabolic process catalyzed by bioanodes following the reductive reaction, which explained the 0.034 mM d(-1) defluorination in R3, but negligible defluorination in controls. Taken together, these results revealed a sequentially combined reduction and oxidation mechanism in the thermophilic BECS for p-FNB removal. Moreover, the enrichment of Betaproteobacteria and uniquely selected Bacilli in R3 were probably functional populations for p-FNB degradation. PMID:27268793

  16. Biological reduction of nitric oxide in aqueous Fe(II)EDTA solutions.

    PubMed

    van der Maas, Peter; van de Sandt, Thomas; Klapwijk, Bram; Lens, Piet

    2003-01-01

    The reduction of nitric oxide (NO) in aqueous solutions of Fe(II)EDTA is one of the core processes in BioDeNOx, an integrated physicochemical and biological technique for NO(x)() removal from industrial flue gases. NO reduction in aqueous solutions of Fe(II)EDTA (20-25 mM, pH 7.2 +/- 0.2) was investigated in batch experiments at 55 degrees C. Reduction of NO to N(2) was found to be biologically catalyzed with nitrous oxide (N(2)O) as an intermediate. Various sludges from full-scale denitrifying and anaerobic reactors were capable to catalyze NO reduction under thermophilic conditions. The NO reduction rate was not affected by the presence of ethanol or acetate. EDTA-chelated Fe(II) was found to be a suitable electron donor for the biological reduction of nitric oxide to N(2), with the concomitant formation of Fe(III)EDTA. In the presence of ethanol, EDTA-chelated Fe(III) was reduced to Fe(II)EDTA. This study strongly indicates that redox cycling of FeEDTA plays an important role in the biological denitrification process within the BioDeNOx concept. PMID:12892497

  17. Fabrication and Characteristics of Reduced Graphene Oxide Produced with Different Green Reductants

    PubMed Central

    Ji, An; Shi, Lina; Zhou, Chen; Cui, Yunqi

    2015-01-01

    There has been an upsurge of green reductants for the preparation of graphene materials taking consideration of human health and the environment in recent years. In this paper, reduced graphene oxides (RGOs) were prepared by chemical reduction of graphene oxide (GO) with three green reductants, L-ascorbic acid (L-AA), D-glucose (D-GLC) and tea polyphenol (TP), and comparatively characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectra, Raman spectra and electrical conductivity analysis. Results showed that all these three reductants were effective to remove oxygen-containing functional groups in GO and restore the electrical conductivity of the obtained RGO. The RGO sample with L-ascorbic acid as a reductant and reduced with the existence of ammonia had the highest electrical conductivity (9.8 S·cm-1) among all the obtained RGO samples. The mechanisms regarding to the reduction of GO and the dispersion of RGO in water were also proposed. It is the good dispersibility of reduced graphene oxide in water that will facilitate its further use in composite materials and conductive ink. PMID:26658644

  18. Fabrication and Characteristics of Reduced Graphene Oxide Produced with Different Green Reductants.

    PubMed

    Xu, Changyan; Shi, Xiaomei; Ji, An; Shi, Lina; Zhou, Chen; Cui, Yunqi

    2015-01-01

    There has been an upsurge of green reductants for the preparation of graphene materials taking consideration of human health and the environment in recent years. In this paper, reduced graphene oxides (RGOs) were prepared by chemical reduction of graphene oxide (GO) with three green reductants, L-ascorbic acid (L-AA), D-glucose (D-GLC) and tea polyphenol (TP), and comparatively characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectra, Raman spectra and electrical conductivity analysis. Results showed that all these three reductants were effective to remove oxygen-containing functional groups in GO and restore the electrical conductivity of the obtained RGO. The RGO sample with L-ascorbic acid as a reductant and reduced with the existence of ammonia had the highest electrical conductivity (9.8 S·cm(-1)) among all the obtained RGO samples. The mechanisms regarding to the reduction of GO and the dispersion of RGO in water were also proposed. It is the good dispersibility of reduced graphene oxide in water that will facilitate its further use in composite materials and conductive ink. PMID:26658644

  19. High rates of anaerobic methane oxidation in freshwater wetlands reduce potential atmospheric methane emissions.

    PubMed

    Segarra, K E A; Schubotz, F; Samarkin, V; Yoshinaga, M Y; Hinrichs, K-U; Joye, S B

    2015-01-01

    The role of anaerobic oxidation of methane (AOM) in wetlands, the largest natural source of atmospheric methane, is poorly constrained. Here we report rates of microbially mediated AOM (average rate=20 nmol cm(-3) per day) in three freshwater wetlands that span multiple biogeographical provinces. The observed AOM rates rival those in marine environments. Most AOM activity may have been coupled to sulphate reduction, but other electron acceptors remain feasible. Lipid biomarkers typically associated with anaerobic methane-oxidizing archaea were more enriched in (13)C than those characteristic of marine systems, potentially due to distinct microbial metabolic pathways or dilution with heterotrophic isotope signals. On the basis of this extensive data set, AOM in freshwater wetlands may consume 200 Tg methane per year, reducing their potential methane emissions by over 50%. These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources. PMID:26123199

  20. Redox Potentials, Laccase Oxidation, and Antilarval Activities of Substituted Phenols

    PubMed Central

    Prasain, Keshar; Nguyen, Thi D. T.; Gorman, Maureen J.; Barrigan, Lydia M.; Peng, Zeyu; Kanost, Michael R.; Syed, Lateef U.; Li, Jun; Zhu, Kun Yan; Hua, Duy H.

    2012-01-01

    Laccases are copper-containing oxidases that are involved in sclerotization of the cuticle of mosquitoes and other insects. Oxidation of exogenous compounds by insect laccases may have the potential to produce reactive species toxic to insects. We investigated two classes of substituted phenolic compounds, halogenated di- and trihydroxybenzenes and substituted di-tert-butylphenols, on redox potential, oxidation by laccase and effects on mosquito larval growth. An inverse correlation between the oxidation potentials and laccase activity of halogenated hydroxybenzenes was found. Substituted di-tert-butylphenols however were found to impact mosquito larval growth and survival. In particular, 2,4-di-tert-butyl-6-(3-methyl-2-butenyl)phenol (15) caused greater than 98% mortality of Anopheles gambiae larvae in a concentration of 180 nM, whereas 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methylpropanal oxime (13) and 6,8-di-tert-butyl-2,2-dimethyl-3,4-dihydro-2H-chromene (33) caused 93% and 92% mortalities in concentrations of 3.4 and 3.7 μM, respectively. Larvae treated with di-tert-butylphenolic compounds died just before pupation. PMID:22300888

  1. Oxidative stress and abdominal aortic aneurysm: potential treatment targets.

    PubMed

    Emeto, Theophilus I; Moxon, Joseph V; Au, Minnie; Golledge, Jonathan

    2016-03-01

    Abdominal aortic aneurysm (AAA) is a significant cause of mortality in older adults. A key mechanism implicated in AAA pathogenesis is inflammation and the associated production of reactive oxygen species (ROS) and oxidative stress. These have been suggested to promote degradation of the extracellular matrix (ECM) and vascular smooth muscle apoptosis. Experimental and human association studies suggest that ROS can be favourably modified to limit AAA formation and progression. In the present review, we discuss mechanisms potentially linking ROS to AAA pathogenesis and highlight potential treatment strategies targeting ROS. Currently, none of these strategies has been shown to be effective in clinical practice. PMID:26814202

  2. Characterization study of polycrystalline tin oxide surfaces before and after reduction in CO

    NASA Technical Reports Server (NTRS)

    Drawdy, Jean E.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

    1990-01-01

    Polycrystalline tin oxide surfaces have been examined before and after reduction in 40 Torr of CO at 100 and 175 C using Auger electron spectroscopy (AES), electron spectroscopy for chemical analysis (ESCA), ion scattering spectroscopy (ISS) and electron stimulated desorption (ESD). The changes in the surface composition and chemical states of the surface species generally are subtle for the reductive conditions used. However, significant changes do occur with regard to the amounts and the chemical forms of the hydrogen-containing species remaining after both the 100 and 175 C reductions.

  3. Bacterial reduction of N-oxides of tobacco-specific nitrosamines (TSNA).

    PubMed

    Atawodi, S E; Richter, E

    1996-04-01

    1. Contrary to established metabolic pattern, a recent investigation of NNK metabolism produced in rat urine higher levels of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) than their N-oxides, suggesting that reconversion of N-oxides could occur after urine formation. 2. To verify the possible role of bacteria in the reduction of NNK-N-oxide and NNAL-N-oxide to their respective parent compounds, NNK and NNAL, in smokers with urinary tract infection (UTI), the N-oxides were isolated from the urine of rats treated with [5-3H]NNK and individually incubated at 37 degrees C with ten bacterial species in sterile human urine under different pH regimens. After incubation with the bacteria, aliquots of culture media were analyzed by high pressure liquid chromatography (HPLC) with radiochemical detection. 3. Escherichia coli, Enterobacter cloacae, Klebsiella pneumoniae and Proteus mirabilis possessed varying capacity to regenerate NNK and NNAL from their N-oxides while others showed no detectable reductive capability within 24 h. 4. This result constitutes the first experimental evidence that in tobacco users with concomitant UTI, bacterial regeneration of the procarcinogenic NNK and NNAL from their N-oxides could occur in the bladder leading to increased carcinogen burden in these individuals. PMID:8845223

  4. Relationship Between Iron Whisker Growth and Doping Amount of Oxide During Fe2O3 Reduction

    NASA Astrophysics Data System (ADS)

    Gong, Xuzhong; Zhao, Zhilong; Wang, Zhi; Zhang, Ben; Guo, Lei; Guo, Zhancheng

    2016-04-01

    Iron whisker growth during Fe2O3 doped with oxide reduced by CO was investigated by using in situ observation and scanning electron microscopy. The results indicated that the minimum doping amount (MDA) of various oxides, hindering the iron whisker growth, was different. The MDA of Al2O3, Li2O, Na2O, and K2O was 0.5, 0.4, 4, and 12 pct, respectively. From the reduction rate, it was found that Li2O, MgO, and Al2O3 had some suppressive effects on the Fe2O3 reduction process, thus, confining the growth of iron whisker. However, other oxides had some catalytic effects on the Fe2O3 reduction process (Fe2O3-Fe3O4-FeO-Fe), such as CaO, SrO, BaO, Na2O, and K2O. As long as their doping amount was enough, these oxides could inhibit the diffusion of the Fe atom. When the metal ionic radius in doped oxide was bigger than that of Fe3+, such as Ca2+, Sr2+, Ba2+, Na+, and K+, there were lots of spaces left in Fe2O3 doped with oxide after reduction, improving Fe atom diffusion. Consequently, their MDA was more than that of small radius to restrain the growth of iron whisker. Finally, the relationship between corresponding metal ionic radius, electron layer number, valence electron number, and MDA of oxide was expressed by using data fitting as follows: N_{{{{A}}y {{O}}x }} = 1.3 × 10^{ - 5} × {r_{{{{A}}^{x + } }}2 × √{n_{{{{A}}^{x + } }} } }/{f_{q }}

  5. Pyrite oxidation and reduction - Molecular orbital theory considerations. [for geochemical redox processes

    NASA Technical Reports Server (NTRS)

    Luther, George W., III

    1987-01-01

    In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

  6. Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: II. Kinetic analysis

    NASA Astrophysics Data System (ADS)

    Sinder, M.; Burshtein, Z.; Pelleg, J.

    2014-04-01

    We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. In the companion part I paper we provide thermodynamic analyses yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons, as functions of the ambient oxygen pressure. In the present companion part II paper we provide time dependent concentration profiles of the various species and reaction rate profiles. The diffusion exhibits a complex behavior; under some conditions, it may be described by a constant diffusivity, and is symmetric with respect to oxidation and reduction. However, under a wide range of conditions, the ionic state changes are highly asymmetric with respect to oxidation and reduction. For example, in the case of a neutral vacancy, a very narrow reaction front may establish during reduction. In the inverse (oxidation) process, however, the different species' profiles are quite smooth.

  7. Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

    PubMed

    Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

    2016-05-01

    Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments. PMID:26762391

  8. Maillard reaction, mitochondria and oxidative stress: potential role of antioxidants.

    PubMed

    Edeas, M; Attaf, D; Mailfert, A-S; Nasu, M; Joubet, R

    2010-06-01

    Glycation and oxidative stress are two important processes known to play a key role in complications of many disease processes. Oxidative stress, either via increasing reactive oxygen species (ROS), or by depleting the antioxidants may modulate the genesis of early glycated proteins in vivo. Maillard Reactions, occur in vivo as well as in vitro and are associated with the chronic complications of diabetes, aging and age-related diseases. Hyperglycaemia causes the autoxidation of glucose, glycation of proteins, and the activation of polyol metabolism. These changes facilitate the generation of reactive oxygen species and decrease the activity of antioxidant enzymes such as Cu,Zn-superoxide dismutase, resulting in a remarkable increase of oxidative stress. A large body of evidence indicates that mitochondria alteration is involved and plays a central role in various oxidative stress-related diseases. The damaged mitochondria produce more ROS (increase oxidative stress) and less ATP (cellular energy) than normal mitochondria. As they are damaged, they cannot burn or use glucose or lipid and cannot provide cell with ATP. Further, glucose, amino acids and lipid will not be correctly used and will accumulate outside the mitochondria; they will undergo more glycation (as observed in diabetes, obesity, HIV infection and lipodystrophia). The objective of this paper is to discuss how to stop the vicious circle established between oxidative stress, Maillard Reaction and mitochondria. The potential application of some antioxidants to reduce glycation phenomenon and to increase the antioxidant defence system by targeting mitochondria will be discussed. Food and pharmaceutical companies share the same challenge, they must act now, urgently and energetically. PMID:20031340

  9. Multifunctional Low-Pressure Turbine for Core Noise Reduction, Improved Efficiency, and Nitrogen Oxide (NOx) Reduction

    NASA Technical Reports Server (NTRS)

    Miller, Christopher J.; Shyam, Vikram; Rigby, David L.

    2013-01-01

    This work studied the feasibility of using Helmholtz resonator cavities embedded in low-pressure-turbine (LPT) airfoils to (1) reduce core noise by damping acoustic modes; (2) use the synthetic jets produced by the liner hole acoustic oscillations to improve engine efficiency by maintaining turbulent attached flow in the LPT at low-Reynolds-number cruise conditions; and (3) reduce engine nitrogen oxide emissions by lining the internal cavities with materials capable of catalytic conversion. Flat plates with embedded Helmholtz resonators, designed to resonate at either 3000 or at 400 Hz, were simulated using computational fluid dynamics. The simulations were conducted for two inlet Mach numbers, 0.25 and 0.5, corresponding to Reynolds numbers of 90 000 and 164 000 based on the effective chordwise distance to the resonator orifice. The results of this study are (1) the region of acoustic treatment may be large enough to have a benefit; (2) the jets may not possess sufficient strength to reduce flow separation (based on prior work by researchers in the flow control area); and (3) the additional catalytic surface area is not exposed to a high velocity, so it probably does not have any benefit.

  10. Explosive thermal reduction of graphene oxide-based materials: mechanism and safety implications

    PubMed Central

    Qiu, Yang; Guo, Fei; Hurt, Robert; Külaots, Indrek

    2014-01-01

    Thermal reduction of graphene oxide or graphite oxide (GO) is an important processing step in the fabrication of many graphene-based materials and devices. Here we show that some bulk solid GO samples can undergo explosive decomposition when small samples are heated slowly in inert gas environments, while others do not. These micro-explosions can occur for samples as small as few milligrams and are sufficiently energetic to cause laboratory equipment damage. Thermochemical analysis methods are used to understand the factors that lead to the explosive reduction mode. The studies show that the explosive mode of reduction is caused by the exothermicity of GO reduction coupled with a threshold sample mass/size that causes heat and mass transfer limitations leading to local temperature rise and a thermal runaway reaction. The explosive mode of reduction is not caused or promoted by interstitial water, and its onset temperature can be lowered by immersion in potassium hydroxide solution. By allowing early release of internal gas pressure, the explosive mode reduces the extent of surface area development in GO exfoliation from an optimum value of 1470 m2g−1 obtained under non-explosive reduction conditions. Explosive reduction of bulk GO poses industrial safety hazards during large-scale storage, handling, and processing. PMID:25018560

  11. Synthesis of reduced graphene oxide (rGO) via chemical reduction

    SciTech Connect

    Thakur, Alpana Rangra, V. S.; Kumar, Sunil

    2015-05-15

    Natural flake Graphite was used as the starting material for the graphene synthesis. In the first step flake graphite was treated with oxidizing agents under vigorous conditions to obtain graphite oxide. Layered graphite oxide decorated with oxygen has large inter-layer distance leading easy exfoliation into single sheets by ultrasonication giving graphene oxide. In the last step exfoliated graphene oxide sheets were reduced slowly with the help of reducing agent to obtain fine powder which is labeled as reduced graphene oxide (rGO). This rGO was further characterized by X-Ray Diffraction (XRD), Scanning Tunneling Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy techniques. XRD pattern shows peaks corresponding to (002) graphitic lattice planes indicating the formation of network of sp{sup 2} like carbon structure. SEM images show the ultrathin, wrinkled, paper-like morphology of graphene sheets. IR study shows that the graphite has been oxidized to graphite oxide with the presence of various absorption bands confirming the presence of oxidizing groups. The FTIR spectrum of rGO shows no sharp peaks confirming the efficient reduction of rGO. The Raman spectrum shows disorder in the graphene sheets.

  12. Synthesis of reduced graphene oxide (rGO) via chemical reduction

    NASA Astrophysics Data System (ADS)

    Thakur, Alpana; Kumar, Sunil; Rangra, V. S.

    2015-05-01

    Natural flake Graphite was used as the starting material for the graphene synthesis. In the first step flake graphite was treated with oxidizing agents under vigorous conditions to obtain graphite oxide. Layered graphite oxide decorated with oxygen has large inter-layer distance leading easy exfoliation into single sheets by ultrasonication giving graphene oxide. In the last step exfoliated graphene oxide sheets were reduced slowly with the help of reducing agent to obtain fine powder which is labeled as reduced graphene oxide (rGO). This rGO was further characterized by X-Ray Diffraction (XRD), Scanning Tunneling Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy techniques. XRD pattern shows peaks corresponding to (002) graphitic lattice planes indicating the formation of network of sp2 like carbon structure. SEM images show the ultrathin, wrinkled, paper-like morphology of graphene sheets. IR study shows that the graphite has been oxidized to graphite oxide with the presence of various absorption bands confirming the presence of oxidizing groups. The FTIR spectrum of rGO shows no sharp peaks confirming the efficient reduction of rGO. The Raman spectrum shows disorder in the graphene sheets.

  13. Reduction of coherence of the human brain electric potentials

    NASA Astrophysics Data System (ADS)

    Novik, Oleg; Smirnov, Fedor

    Plenty of technological processes are known to be damaged by magnetic storms. But technology is controlled by men and their functional systems may be damaged as well. We are going to consider the electro-neurophysiological aspect of the general problem: men surrounded by physical fields including ones of cosmic origination. Magnetic storms’ influence had been observed for a group of 13 students (practically healthy girls and boys from 18 to 23 years old, Moscow). To control the main functional systems of the examinees, their electroencephalograms (EEG) were being registered along with electrocardiograms, respiratory rhythms, arterial blood pressure and other characteristics during a year. All of these characteristics, save for the EEG, were within the normal range for all of the examinees during measurements. According to the EEG investigations by implementation of the computer proof-reading test in absence of magnetic storms, the values of the coherence function of time series of the theta-rhythm oscillations (f = 4 - 7.9 Hz, A = 20 μV) of electric potentials of the frontal-polar and occipital areas of the head belong to the interval [0.3, 0.8] for all of the students under investigation. (As the proof-reading test, it was necessary to choose given symbols from a random sequence of ones demonstrated at a monitor and to enter the number of the symbols discovered in a computer. Everyone was known that the time for determination of symbols is unlimited. On the other hand, nobody was known that the EEG and other registrations mentioned are connected with electromagnetic geophysical researches and geomagnetic storms). Let us formulate the main result: by implementation of the same test during a magnetic storm, 5 ≤ K ≤ 6, or no later then 24 hours after its beginning (different types of moderate magnetic storms occurred, the data of IZMIRAN were used), the values of the theta-rhythm frontal - occipital coherence function of all of the students of the group under

  14. FINAL REPORT. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION

    EPA Science Inventory

    The objectives of this research project were to refine existing models of microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of the subsurface. Novel experimenta...

  15. Advanced Experiment Analysis of controls on Microbial FE(III) Oxide Reduction

    SciTech Connect

    Roden, Eric E.; Urrutia, Matilde M.

    1999-06-01

    Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting the ability of these organisms to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine our quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction activity.

  16. The Simulation of an Oxidation-Reduction Titration Curve with Computer Algebra

    ERIC Educational Resources Information Center

    Whiteley, Richard V., Jr.

    2015-01-01

    Although the simulation of an oxidation/reduction titration curve is an important exercise in an undergraduate course in quantitative analysis, that exercise is frequently simplified to accommodate computational limitations. With the use of readily available computer algebra systems, however, such curves for complicated systems can be generated…

  17. Low temperature process for the reduction of nitrogen oxides in an effluent

    SciTech Connect

    Epperly, W.R.; Sullivan, J.C.; Sprague, B.N.

    1989-10-10

    This patent describes a process for the reduction of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprising introducing a treatment agent which comprises an ammonium salt selected from the group consisting of triammonium citrate and ammonium formate into the effluent at an effluent temperature below 1300{sup 0}F.

  18. Synthesis of carbon-encapsulated iron nanoparticles via solid state reduction of iron oxide nanoparticles

    SciTech Connect

    Bystrzejewski, M.

    2011-06-15

    The encapsulation of iron nanoparticles in protective carbon cages leads to unique hybrid core-shell nanomaterials. Recent literature reports suggest that such nanocomposites can be obtained in a relatively simple process involving the solid state carbothermal reduction of iron oxide nanoparticles. This approach is very attractive because it does not require advanced equipment and consumes less energy in comparison to widely used plasma methods. The presented more-in-depth study shows that the carbothermal approach is sensitive to temperature and the process yield strongly depends on the morphology and crystallinity of the carbon material used as a reductant. - Graphical abstract: Reduction of iron oxide nanoparticles by carbon black at 1200 deg. C yields well crystallized carbon-encapsulated iron nanoparticles. Highlights: > Carbon-encapsulated iron nanoparticles were synthesized by carbothermal reduction of iron oxide nanoparticles. > The process has the highest selectivity at 1200 C. > Lower temperatures result in iron oxide nanoparticles wrapped in carbon matrix. > The encapsulation rate of Fe at 1200 deg. C was found to be 15%.

  19. In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies

    NASA Technical Reports Server (NTRS)

    Keith, Amy; Glasgow, Jason; McCaleh, Rececca C. (Technical Monitor)

    2001-01-01

    This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

  20. Some Aspects of Oxidation-Reduction Reactions under Carbon-Bearing Flux Welding

    NASA Astrophysics Data System (ADS)

    Kryukov, R. E.; Kozyrev, N. A.; Galevsky, G. V.; Bendre, Y. V.; Goryushkin, V. F.; Valuev, D. V.

    2015-09-01

    The authors have completed thermodynamic calculations of oxidation-reduction processes under submerged arc welding with application of carbon containing additive. The calculations have shown that carbon, due to its high reducing properties under T = 1950 - 2200 K, introduced into the system can significantly decrease the amount of non-metallic inclusions in the weld metal and so improve its mechanical properties.

  1. CATALYTIC REDUCTION OF NITROGEN OXIDES WITH AMMONIA: UTILITY PILOT PLANT OPERATION

    EPA Science Inventory

    The report describes work to demonstrate, on a utility pilot plant scale, the performance, reliability, and practicability of reducing nitrogen oxides (NOx) emissions from steam boilers by reduction of NOx with ammonia over a platinum catalyst. A utility pilot plant treating a sl...

  2. Two-Electron Reduction versus One-Electron Oxidation of the Type 3 Pair in the Multicopper Oxidases.

    PubMed

    Kjaergaard, Christian H; Jones, Stephen M; Gounel, Sébastien; Mano, Nicolas; Solomon, Edward I

    2015-07-15

    Multicopper oxidases (MCOs) utilize an electron shuttling Type 1 Cu (T1) site in conjunction with a mononuclear Type 2 (T2) and a binuclear Type 3 (T3) site, arranged in a trinuclear copper cluster (TNC), to reduce O2 to H2O. Reduction of O2 occurs with limited overpotential indicating that all the coppers in the active site can be reduced via high-potential electron donors. Two forms of the resting enzyme have been observed in MCOs: the alternative resting form (AR), where only one of the three TNC Cu's is oxidized, and the resting oxidized form (RO), where all three TNC Cu's are oxidized. In contrast to the AR form, we show that in the RO form of a high-potential MCO, the binuclear T3 Cu(II) site can be reduced via the 700 mV T1 Cu. Systematic spectroscopic evaluation reveals that this proceeds by a two-electron process, where delivery of the first electron, forming a high energy, metastable half reduced T3 state, is followed by the rapid delivery of a second energetically favorable electron to fully reduce the T3 site. Alternatively, when this fully reduced binuclear T3 site is oxidized via the T1 Cu, a different thermodynamically favored half oxidized T3 form, i.e., the AR site, is generated. This behavior is evaluated by DFT calculations, which reveal that the protein backbone plays a significant role in controlling the environment of the active site coppers. This allows for the formation of the metastable, half reduced state and thus the complete reductive activation of the enzyme for catalysis. PMID:26075678

  3. Two-electron Reduction versus One-electron Oxidation of the Type 3 Pair in the Multicopper Oxidases

    PubMed Central

    Kjaergaard, Christian H.; Jones, Stephen M.; Gounel, Sébastien; Mano, Nicolas; Solomon, Edward I.

    2015-01-01

    Multicopper Oxidases (MCOs) utilize an electron shuttling Type 1 Cu (T1) site in conjunction with a mononuclear Type 2 (T2) and a binuclear Type 3 (T3) site, arranged in a trinuclear copper cluster (TNC), to reduce O2 to H2O. Reduction of O2 occurs with limited overpotential indicating that all the coppers in the active site can be reduced via high-potential electron donors. Two forms of the resting enzyme have been observed in MCOs: the Alternative Resting form (AR), where only one of the three TNC Cu’s is oxidized, and the Resting Oxidized form (RO), where all three TNC Cu’s are oxidized. In contrast to the AR form, we show that in the RO form of a high-potential MCO, the binuclear T3 Cu(II) site can be reduced via the 700 mV T1 Cu. Systematic spectroscopic evaluation reveals that this proceeds by a two-electron process, where delivery of the first electron, forming a high energy, meta-stable half reduced T3 state, is followed by the rapid delivery of a second energetically favorable electron to fully reduce the T3 site. Alternatively, when this fully reduced binuclear T3 site is oxidized via the T1 Cu, a different thermodynamically favored half oxidized T3 form, i.e. the AR site, is generated. This behavior is evaluated by DFT calculations, which reveal that the protein backbone plays a significant role in controlling the environment of the active site coppers. This allows for the formation of the meta-stable, half reduced state and thus the complete reductive activation of the enzyme for catalysis. PMID:26075678

  4. Flat-Band Potentials of Molecularly Thin Metal Oxide Nanosheets.

    PubMed

    Xu, Pengtao; Milstein, Tyler J; Mallouk, Thomas E

    2016-05-11

    Exfoliated nanosheets derived from Dion-Jacobson phase layer perovskites (TBAxH1-xA2B3O10, A = Sr, Ca, B = Nb, Ta) were grown layer-by-layer on fluorine-doped tin oxide and gold electrode surfaces. Electrochemical impedance spectra (EIS) of the five-layer nanosheet films in contact with aqueous electrolyte solutions were analyzed by the Mott-Schottky method to obtain flat-band potentials (VFB) of the oxide semiconductors as a function of pH. Despite capacitive contributions from the electrode-solution interface, reliable values could be obtained from capacitance measurements over a limited potential range near VFB. The measured values of VFB shifted -59 mV/pH over the pH range of 4-8 and were in close agreement with the empirical correlation between conduction band-edge potentials and optical band gaps proposed by Matsumoto ( J. Solid State Chem. 1996, 126 (2), 227-234 ). Density functional theory calculations showed that A-site substitution influenced band energies by modulating the strength of A-O bonding, and that subsitution of Ta for Nb on B-sites resulted in a negative shift of the conduction band-edge potential. PMID:27102083

  5. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and pattern

  6. Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets

    EIA Publications

    2011-01-01

    This report is the Energy Information Administration's (EIA) initial effort to provide information and analysis on the potential impacts on petroleum product markets from reductions in Northeast petroleum refining activity.

  7. Filtrates and Residues. Galvanic Cells and the Standard Reduction Potential Table.

    ERIC Educational Resources Information Center

    Tanis, David O.

    1990-01-01

    Presented is an activity designed to introduce introductory chemistry students to the standard reduction potential table. Included are lists of equipment and reagents, procedures, sample worksheets, and teaching directions. (CW)

  8. Intermolecular potential energy surface and thermophysical properties of ethylene oxide

    SciTech Connect

    Crusius, Johann-Philipp Hassel, Egon; Hellmann, Robert; Bich, Eckard

    2014-10-28

    A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

  9. Intermolecular potential energy surface and thermophysical properties of ethylene oxide.

    PubMed

    Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

    2014-10-28

    A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide. PMID:25362314

  10. Plasma in-liquid method for reduction of zinc oxide in zinc nanoparticle synthesis

    NASA Astrophysics Data System (ADS)

    Amaliyah, Novriany; Mukasa, Shinobu; Nomura, Shinfuku; Toyota, Hiromichi; Kitamae, Tomohide

    2015-02-01

    Metal air-batteries with high-energy density are expected to be increasingly applied in electric vehicles. This will require a method of recycling air batteries, and reduction of metal oxide by generating plasma in liquid has been proposed as a possible method. Microwave-induced plasma is generated in ethanol as a reducing agent in which zinc oxide is dispersed. Analysis by energy-dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD) reveals the reduction of zinc oxide. According to images by transmission electron microscopy (TEM), cubic and hexagonal metallic zinc particles are formed in sizes of 30 to 200 nm. Additionally, spherical fiber flocculates approximately 180 nm in diameter are present.

  11. Reduction Kinetics of Electric Arc Furnace Oxidizing Slag by Al-Fe Alloy

    NASA Astrophysics Data System (ADS)

    Lee, Jaehong; Oh, Joon Seok; Lee, Joonho

    2016-07-01

    Effects of temperature and slag basicity on the reduction rate of iron oxide in molten synthetic electric arc furnace oxidizing slag by Al-40 wt.%Fe alloy was investigated. An alloy sample was dropped into molten slag in an MgO crucible. When the initial slag temperature was 1723 K, there was no reduction. However, when the initial slag temperature was 1773 K and the slag basicity was 1.1, the reduction was initiated and the temperature of the slag rapidly increased. When the slag basicity was 1.1, increasing the initial slag temperature from 1773 K to 1823 K increases the reaction rate. As the slag basicity increased from 1.1 to 1.4 at 1773 K, the reaction rate increased. From SEM analysis, it was found that an Al2O3 or a spinel phase at the slag-metal interface inhibited the reaction at a lower temperature and a lower slag basicity.

  12. A One-Step, Solvothermal Reduction Method for Producing Reduced Graphene Oxide Dispersions in Organic Solvents

    PubMed Central

    Dubin, Sergey; Gilje, Scott; Wang, Kan; Tung, Vincent C.; Cha, Kitty; Hall, Anthony S.; Farrar, Jabari; Varshneya, Rupal; Yang, Yang; Kaner, Richard B.

    2014-01-01

    Refluxing graphene oxide (GO) in N-methyl-2-pyrrolidinone (NMP) results in deoxygenation and reduction to yield a stable colloidal dispersion. The solvothermal reduction is accompanied by a color change from light brown to black. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images of the product confirm the presence of single sheets of the solvothermally reduced graphene oxide (SRGO). X-ray photoelectron spectroscopy (XPS) of SRGO indicates a significant increase in intensity of the C=C bond character, while the oxygen content decreases markedly after the reduction is complete. X-ray diffraction analysis of SRGO shows a single broad peak at 26.24° 2θ (3.4 Å), confirming the presence of graphitic stacking of reduced sheets. SRGO sheets are redispersible in a variety of organic solvents, which may hold promise as an acceptor material for bulk heterojunction photovoltaic cells, or electromagnetic interference shielding applications. PMID:20586422

  13. Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

    PubMed

    Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

    2015-11-01

    A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder. PMID:25871933

  14. Study on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos.

    PubMed

    Chen, Shifu; Cao, Gengyu

    2005-09-01

    In this paper, dichromate and dichlorvos are selected as the deputies of inorganic and organic pollutants, respectively, and TiO2/beads is used as a photocatalyst. The effects of various parameters, such as the amount of the photocatalyst, H2O2 concentration, metal ions, anions, pH value, and organic compounds on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos are studied. From the studies, the differences of the parameters effect on the photocatalytic degradation of organic and inorganic pollutants are obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g cm(-3) for the photocatalytic reactions. With the addition of a small amount of H2O2, the photocatalytic reduction of dichromate is inhibited while the photocatalytic oxidation of dichlorvos is accelerated. With the addition of trace amounts of Fe3+ or Cu2+, both the reactions are accelerated, and with the addition of Zn2+ and Na+, no obvious effects on the reactions are observed. Acidic solution is favorable for the photocatalytic reduction of dichromate; and acidic and alkaline solutions are favorable for the photocatalytic oxidation of dichlorvos. Adding SO4(2-), the photocatalytic oxidation is accelerated and adding Cl- the reaction is inhibited; and with the addition of trace amounts of SO4(2-), Cl- and NO3-, no obvious effects on the photocatalytic reduction of dichromate are observed. With the addition of methanol and toluene, the photocatalytic reduction of dichromate is accelerated, and the photocatalytic oxidation of dichlorvos is inhibited. The possible roles of the additives on the reactions are also discussed. PMID:16018902

  15. Biostimulation of Iron Reduction and Subsequent Oxidation of Sediment Containing Fe-silicates and Fe-oxides: Effect of Redox Cycling on Fe(III) Bioreduction

    SciTech Connect

    Komlos, John; Kukkadapu, Ravi K.; Zachara, John M.; Jaffe, Peter R.

    2007-07-01

    Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day column experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.

  16. Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets

    EIA Publications

    2012-01-01

    Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets is an update to a previous Energy Information Administration (EIA) report, Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets, released in December 2011. This update analyzes possible market responses and impacts in the event Sunoco's Philadelphia refinery closes this summer, in addition to the recently idled refineries on the East Coast and in the U.S. Virgin Islands.

  17. Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  18. Reduction and persulfate oxidation of nitro explosives in contaminated soils using Fe-bearing materials.

    PubMed

    Oh, Seok-Young; Yoon, Hyun-Su; Jeong, Tae-Yong; Kim, Sang Don; Kim, Dong-Wook

    2016-07-13

    The oxidative and reductive transformation of nitro explosives in contaminated soils with Fe-bearing materials and persulfate (S2O8(2-)) was examined via batch experiments. Zero-valent cast iron [Fe(0)], steel dust from a steel manufacturing plant, and FeS rapidly reduced 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in soil under anaerobic conditions as long as a sufficient amount of water was present. The Fe-bearing materials also effectively activated persulfate to enhance the oxidative transformation of TNT and RDX in soil-water systems. Kinetically, reductive and oxidative transformations removed more than 90% of the explosives from a soil-water system within 5 h under the given conditions. Pseudo-first-order rates in the range of 0.7-23.4 h(-1) were observed. By increasing the concentration of persulfate or Fe-bearing materials, the oxidative transformation could be promoted. Treated soils via redox reactions using the Fe-bearing materials did not show significant toxicity, except for the case of TNT-contaminated soils oxidized by FeS-assisted persulfate. Considering the kinetics of explosive degradation and the toxicity of treated wastewaters and soils, Fe(0) or steel dust-assisted persulfate oxidation may be a safe option as an ex situ remediation process for the treatment of explosive-contaminated soils. PMID:27327861

  19. Conifer somatic embryogenesis: improvements by supplementation of medium with oxidation-reduction agents.

    PubMed

    Pullman, Gerald S; Zeng, Xiaoyan; Copeland-Kamp, Brandi; Crockett, Jonathan; Lucrezi, Jacob; May, Sheldon W; Bucalo, Kylie

    2015-02-01

    A major barrier to the commercialization of somatic embryogenesis technology in loblolly pine (Pinus taeda L.) is recalcitrance of some high-value crosses to initiate embryogenic tissue (ET) and continue early-stage somatic embryo growth. Developing initiation and multiplication media that resemble the seed environment has been shown to decrease this recalcitrance. Glutathione (GSH), glutathione disulfide (GSSG), ascorbic acid and dehydroascorbate analyses were performed weekly throughout the sequence of seed development for female gametophyte and zygotic embryo tissues to determine physiological concentrations. Major differences in stage-specific oxidation-reduction (redox) agents were observed. A simple bioassay was used to evaluate potential growth-promotion of natural and inorganic redox agents added to early-stage somatic embryo growth medium. Compounds showing statistically significant increases in early-stage embryo growth were then tested for the ability to increase initiation of loblolly pine. Low-cost reducing agents sodium dithionite and sodium thiosulfate increased ET initiation for loblolly pine and Douglas fir (Mirb) Franco. Germination medium supplementation with GSSG increased somatic embryo germination. Early-stage somatic embryos grown on medium with or without sodium thiosulfate did not differ in GSH or GSSG content, suggesting that sodium thiosulfate-mediated growth stimulation does not involve GSH or GSSG. We have developed information demonstrating that alteration of the redox environment in vitro can improve ET initiation, early-stage embryo development and somatic embryo germination in loblolly pine. PMID:25716878

  20. Palladium and gold nanotubes as oxygen reduction reaction and alcohol oxidation reaction catalysts in base.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2014-06-01

    Palladium (PdNTs) and gold nanotubes (AuNTs) were synthesized by the galvanic displacement of silver nanowires. PdNTs and AuNTs have wall thicknesses of 6 nm, outer diameters of 60 nm, and lengths of 5-10 and 5-20 μm, respectively. Rotating disk electrode experiments showed that the PdNTs and AuNTs have higher area normalized activities for the oxygen reduction reaction (ORR) than conventional nanoparticle catalysts. The PdNTs produced an ORR area activity that was 3.4, 2.2, and 3.7 times greater than that on carbon-supported palladium nanoparticles (Pd/C), bulk polycrystalline palladium, and carbon-supported platinum nanoparticles (Pt/C), respectively. The AuNTs produced an ORR area activity that was 2.3, 9.0, and 2.0 times greater than that on carbon-supported gold nanoparticles (Au/C), bulk polycrystalline gold, and Pt/C, respectively. The PdNTs also had lower onset potentials than Pd/C and Pt/C for the oxidation of methanol (0.236 V), ethanol (0.215 V), and ethylene glycol (0.251 V). In comparison to Pt/C, the PdNTs and AuNTs further demonstrated improved alcohol tolerance during the ORR. PMID:24757078

  1. Amino-modified cellulose nanocrystals with adjustable hydrophobicity from combined regioselective oxidation and reductive amination.

    PubMed

    Sirviö, Juho Antti; Visanko, Miikka; Laitinen, Ossi; Ämmälä, Ari; Liimatainen, Henrikki

    2016-01-20

    The controlled revision of surface properties to alter the hydrophobic features of nanocellulose is a potential technique to obtain materials for many novel applications and to replace oil-based materials acting as amphiphilic polyelectrolytes, among others. In this study, linear amines with increasing chain length were used to adjust the hydrophobicity of amphiphilic cellulose nanocrystals (CNCs). Methyl-, ethyl-, n-propyl-, n-butyl-, n-pentylamine, and n-hexylamine were introduced into a cellulose backbone using combined periodate oxidation and reductive amination in an aqueous environment. A high-pressure homogenizer was used to liberate a highly transparent (over 85% at visible light range) nanocrystal dispersion containing CNCs with a length of 73-131 nm and a width of 5-6 nm. All of the CNCs had similar charge density but the hydrophobicity, indicated by the contact angle measurement from the films, increased gradually from 64° to 109° as a function of amine chain length. Thus, this study demonstrated the fabrication of uniform, amphiphilic nanosized polyelectrolytes with modifiable hydrophobicity. PMID:26572390

  2. Protein-bound acrolein: Potential markers for oxidative stress

    PubMed Central

    Uchida, Koji; Kanematsu, Masamichi; Sakai, Kensuke; Matsuda, Tsukasa; Hattori, Nobutaka; Mizuno, Yoshikuni; Suzuki, Daisuke; Miyata, Toshio; Noguchi, Noriko; Niki, Etsuo; Osawa, Toshihiko

    1998-01-01

    Acrolein (CH2=CH—CHO) is known as a ubiquitous pollutant in the environment. Here we show that this notorious aldehyde is not just a pollutant, but also a lipid peroxidation product that could be ubiquitously generated in biological systems. Upon incubation with BSA, acrolein was rapidly incorporated into the protein and generated the protein-linked carbonyl derivative, a putative marker of oxidatively modified proteins under oxidative stress. To verify the presence of protein-bound acrolein in vivo, the mAb (mAb5F6) against the acrolein-modified keyhole limpet hemocyanin was raised. It was found that the acrolein-lysine adduct, Nɛ-(3-formyl-3,4-dehydropiperidino)lysine, constitutes an epitope of the antibody. Immunohistochemical analysis of atherosclerotic lesions from a human aorta demonstrated that antigenic materials recognized by mAb5F6 indeed constituted the lesions, in which intense positivity was associated primarily with macrophage-derived foam cells and the thickening neointima of arterial walls. The observations that (i) oxidative modification of low-density lipoprotein with Cu2+ generated the acrolein-low-density lipoprotein adducts and (ii) the iron-catalyzed oxidation of arachidonate in the presence of protein resulted in the formation of antigenic materials suggested that polyunsaturated fatty acids are sources of acrolein that cause the production of protein-bound acrolein. These data suggest that the protein-bound acrolein represents potential markers of oxidative stress and long-term damage to protein in aging, atherosclerosis, and diabetes. PMID:9560197

  3. Oxidation potential and state of some vanadium ores and the relation of woody material to their deposition

    USGS Publications Warehouse

    Pommer, Alfred Michael

    1956-01-01

    Oxidation potential studies with a multiple pH-potential recorder designed and constructed for this purpose demonstrated that some uranium-vanadium ores in the Colorado Plateau were in a reduced state when deposited. Any oxidation which took place occurred after deposition. Experimental and theoretical reducing studies on fresh wood, wood degraded by burial for 450 years, and lignite, indicate that such ores may have been deposited by reduction of oxidized vanadium solutions by woody material. A vanadium (III) mineral, V2O(OH)4, was prepared synthetically by reduction of a vanadium (V) solution with wood. This is the only reported synthesis of any reduced vanadium mineral by any method. It was shown that the origin of almost all vanadium deposits currently of commercial importance involves life processes and products.

  4. Modeling of metal-oxide semiconductor: Analytical bond-order potential for cupric oxide

    NASA Astrophysics Data System (ADS)

    Li, Kun; Yang, Wen; Wei, Ji-Lin; Du, Shi-Wen; Li, Yong-Tang

    2014-04-01

    Atomistic potentials for cupric element and cupric oxide are derived based on the analytical bond-order scheme that was presented by Brenner [Brenner D W, “Erratum: Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films”, Phys. Rev. B 1992, 46 1948]. In this paper, for the pure cupric element, the energy and structural parameters for several bulk phases as well as dimmer structure are well reproduced. The reference data are taken from our density functional theory calculations and the available experiments. The model potential also provides a good description of the bulk properties of various solid structures of cupric oxide compound structures, including cohesive energies, lattice parameters, and elastic constants.

  5. Two Oxidation Sites for Low Redox Potential Substrates

    PubMed Central

    Morales, María; Mate, María J.; Romero, Antonio; Martínez, María Jesús; Martínez, Ángel T.; Ruiz-Dueñas, Francisco J.

    2012-01-01

    Versatile peroxidase shares with manganese peroxidase and lignin peroxidase the ability to oxidize Mn2+ and high redox potential aromatic compounds, respectively. Moreover, it is also able to oxidize phenols (and low redox potential dyes) at two catalytic sites, as shown by biphasic kinetics. A high efficiency site (with 2,6-dimethoxyphenol and p-hydroquinone catalytic efficiencies of ∼70 and ∼700 s−1 mm−1, respectively) was localized at the same exposed Trp-164 responsible for high redox potential substrate oxidation (as shown by activity loss in the W164S variant). The second site, characterized by low catalytic efficiency (∼3 and ∼50 s−1 mm−1 for 2,6-dimethoxyphenol and p-hydroquinone, respectively) was localized at the main heme access channel. Steady-state and transient-state kinetics for oxidation of phenols and dyes at the latter site were improved when side chains of residues forming the heme channel edge were removed in single and multiple variants. Among them, the E140G/K176G, E140G/P141G/K176G, and E140G/W164S/K176G variants attained catalytic efficiencies for oxidation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) at the heme channel similar to those of the exposed tryptophan site. The heme channel enlargement shown by x-ray diffraction of the E140G, P141G, K176G, and E140G/K176G variants would allow a better substrate accommodation near the heme, as revealed by the up to 26-fold lower Km values (compared with native VP). The resulting interactions were shown by the x-ray structure of the E140G-guaiacol complex, which includes two H-bonds of the substrate with Arg-43 and Pro-139 in the distal heme pocket (at the end of the heme channel) and several hydrophobic interactions with other residues and the heme cofactor. PMID:23071108

  6. Potential disruption of protein-protein interactions by graphene oxide.

    PubMed

    Feng, Mei; Kang, Hongsuk; Yang, Zaixing; Luan, Binquan; Zhou, Ruhong

    2016-06-14

    Graphene oxide (GO) is a promising novel nanomaterial with a wide range of potential biomedical applications due to its many intriguing properties. However, very little research has been conducted to study its possible adverse effects on protein-protein interactions (and thus subsequent toxicity to human). Here, the potential cytotoxicity of GO is investigated at molecular level using large-scale, all-atom molecular dynamics simulations to explore the interaction mechanism between a protein dimer and a GO nanosheet oxidized at different levels. Our theoretical results reveal that GO nanosheet could intercalate between the two monomers of HIV-1 integrase dimer, disrupting the protein-protein interactions and eventually lead to dimer disassociation as graphene does [B. Luan et al., ACS Nano 9(1), 663 (2015)], albeit its insertion process is slower when compared with graphene due to the additional steric and attractive interactions. This study helps to better understand the toxicity of GO to cell functions which could shed light on how to improve its biocompatibility and biosafety for its wide potential biomedical applications. PMID:27306022

  7. Potential disruption of protein-protein interactions by graphene oxide

    NASA Astrophysics Data System (ADS)

    Feng, Mei; Kang, Hongsuk; Yang, Zaixing; Luan, Binquan; Zhou, Ruhong

    2016-06-01

    Graphene oxide (GO) is a promising novel nanomaterial with a wide range of potential biomedical applications due to its many intriguing properties. However, very little research has been conducted to study its possible adverse effects on protein-protein interactions (and thus subsequent toxicity to human). Here, the potential cytotoxicity of GO is investigated at molecular level using large-scale, all-atom molecular dynamics simulations to explore the interaction mechanism between a protein dimer and a GO nanosheet oxidized at different levels. Our theoretical results reveal that GO nanosheet could intercalate between the two monomers of HIV-1 integrase dimer, disrupting the protein-protein interactions and eventually lead to dimer disassociation as graphene does [B. Luan et al., ACS Nano 9(1), 663 (2015)], albeit its insertion process is slower when compared with graphene due to the additional steric and attractive interactions. This study helps to better understand the toxicity of GO to cell functions which could shed light on how to improve its biocompatibility and biosafety for its wide potential biomedical applications.

  8. Effect of applied voltage, initial concentration and natural organic matter on sequential reduction/oxidation of nitrobenzene by graphite electrodes

    PubMed Central

    Sun, Mei; Reible, Danny D.; Lowry, Gregory V.; Gregory, Kelvin B.

    2012-01-01

    Carbon electrodes are proposed in reactive sediment caps for in situ treatment of contaminants. The electrodes produce reducing conditions and H2 at the cathode and oxidizing conditions and O2 at the anode. Emplaced perpendicular to seepage flow, the electrodes provide the opportunity for sequential reduction and oxidation of contaminants. The objectives of this study are to demonstrate degradation of nitrobenzene (NB) as a probe compound for sequential electrochemical reduction and oxidation, and to determine the effect of applied voltage, initial concentration and natural organic matter on the degradation rate. In H-cell reactors with graphite electrodes and buffer solution, NB was reduced stoichiometrically to aniline (AN) at the cathode with nitrosobenzene (NSB) as the intermediate. AN was then removed at the anode, faster than the reduction step. No common AN oxidation intermediate was detected in the system. Both the first order reduction rate constants of NB (kNB) and NSB (kNSB) increased with applied voltage between 2V and 3.5 V (when the initial NB concentration was 100 µM, kNB=0.3 d−1 and kNSB=0.04 d−1at 2V; kNB=1.6 d−1 and kNSB=0.64 d−1at 3.5 V) but stopped increasing beyond the threshold of 3.5V. When initial NB concentration decreased from 100 to 5 µM, kNB and kNSB became 9 and 5 times faster, respectively, suggesting that competition for active sites on the electrode surface is an important factor in NB degradation. Presence of natural organic matter (in forms of either humic acid or Anacostia River sediment porewater) decreased kNB while slightly increased kNSB, but only to a limited extent (~factor of 3) for dissolved organic carbon content up to 100 mg/l. These findings suggest that electrode-based reactive sediment capping via sequential reduction/oxidation is a potentially robust and tunable technology for in situ contaminants degradation. PMID:22571797

  9. Real-time monitoring of graphene oxide reduction in acrylic printable composite inks

    NASA Astrophysics Data System (ADS)

    Porro, S.; Giardi, R.; Chiolerio, A.

    2014-06-01

    This work reports the electrical characterization of a water-based graphene oxide/acrylic composite material, which was directly inkjet printed to fabricate dissipative patterns. The graphene oxide filler, which is strongly hydrophilic due to its heavily oxygenated surface and can be readily dispersed in water, was reduced by UV irradiation during photo-curing of the polymeric matrix. The concurrent polymerization of the acrylic matrix and reduction of graphene oxide filler was demonstrated by real-time resistance measurements during UV light irradiation. The presence of graphene filler allowed decreasing the resistance of the pure polymeric matrix by nearly five orders of magnitude. This was explained by the fact that clusters of reduced graphene oxide inside the polymer matrix act as preferential pathways for the mobility of charge carriers, thus leading to an overall decrease of the material's resistance.

  10. Deciphering the Electron Transport Pathway for Graphene Oxide Reduction by Shewanella oneidensis MR-1 ▿†‡

    PubMed Central

    Jiao, Yongqin; Qian, Fang; Li, Yat; Wang, Gongming; Saltikov, Chad W.; Gralnick, Jeffrey A.

    2011-01-01

    We determined that graphene oxide reduction by Shewanella oneidensis MR-1 requires the Mtr respiratory pathway by analyzing a range of mutants lacking these proteins. Electron shuttling compounds increased the graphene oxide reduction rate 3- to 5-fold. These results may help facilitate the use of bacteria for large-scale graphene production. PMID:21602337

  11. Oxygen-assisted reduction of Au species on Au/SiO2 catalyst in room temperature CO oxidation

    SciTech Connect

    Wu, Zili; Zhou, Shenghu; Zhu, Haoguo; Dai, Sheng; Overbury, Steven {Steve} H

    2008-01-01

    An unexpected oxygen-assisted reduction of cationic Au species by CO was found on a Au/SiO2 catalyst at room temperature; CO oxidation activity increases simultaneously with the reduction of Au species, suggesting the key role of metallic Au played in CO oxidation on Au/SiO2.

  12. Reduction of bacteria on spinach, lettuce, and surfaces in food service areas using neutral electrolyzed oxidizing water.

    PubMed

    Guentzel, Jane L; Liang Lam, Kang; Callan, Michael A; Emmons, Stuart A; Dunham, Valgene L

    2008-02-01

    Food safety issues and increases in food borne illnesses have promulgated the development of new sanitation methods to eliminate pathogenic organisms on foods and surfaces in food service areas. Electrolyzed oxidizing water (EO water) shows promise as an environmentally friendly broad spectrum microbial decontamination agent. EO water is generated by the passage of a dilute salt solution ( approximately 1% NaCl) through an electrochemical cell. This electrolytic process converts chloride ions and water molecules into chlorine oxidants (Cl(2), HOCl/ClO(-)). At a near-neutral pH (pH 6.3-6.5), the predominant chemical species is the highly biocidal hypochlorous acid species (HOCl) with the oxidation reduction potential (ORP) of the solution ranging from 800 to 900mV. The biocidal activity of near-neutral EO water was evaluated at 25 degrees C using pure cultures of Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, Listeria monocytogenes, and Enterococcus faecalis. Treatment of these organisms, in pure culture, with EO water at concentrations of 20, 50, 100, and 120ppm total residual chlorine (TRC) and 10min of contact time resulted in 100% inactivation of all five organisms (reduction of 6.1-6.7log(10)CFU/mL). Spray treatment of surfaces in food service areas with EO water containing 278-310ppm TRC (pH 6.38) resulted in a 79-100% reduction of microbial growth. Dip (10min) treatment of spinach at 100 and 120ppm TRC resulted in a 4.0-5.0log(10)CFU/mL reduction of bacterial counts for all organisms tested. Dipping (10min) of lettuce at 100 and 120ppm TRC reduced bacterial counts of E. coli by 0.24-0.25log(10)CFU/mL and reduced all other organisms by 2.43-3.81log(10)CFU/mL. PMID:17993375

  13. Oxidation and Reduction of Sulfite by Chloroplasts and Formation of Sulfite Addition Compounds 1

    PubMed Central

    Dittrich, Andreas P. M.; Pfanz, Hardy; Heber, Ulrich

    1992-01-01

    After exposing intact chloroplasts isolated from spinach (Spinacia oleracea L. cv Yates) and capable of photoreducing CO2 at high rates to different concentrations of radioactive sulfite in the light or in the dark, 35SO2 and H235S were removed from the acidified suspensions in a stream of nitrogen. Remaining activity could be fractionated into sulfate, organic sulfides, and sulfite addition compounds. When chloroplast suspensions contained catalase, superoxide dismutase and O-acetylserine, the oxidation of sulfite to sulfate was slower in the light than the reductive formation of sulfides that exhibited a maximum rate of about 2 micromoles per milligram chlorophyll per hour, equivalent to about 1% of maximum carbon assimilation. Botht the oxidative and the reductive detoxification of sulfite were very slow in the dark. Oxidation was somewhat, but not much, accelerated in the light in the absence of O-acetylserine, which caused a dramatic decrease in the formation of organic sulfides and an equally dramatic increase in the concentration of sulfite addition compounds whose formation was light-dependent. The sulfite addition compounds were not identified. Addition compounds did not accumulate in the dark. In the light, the electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea, diuron, decreased not only the reduction, but also the oxidation of sulfite and the formation of addition compounds. PMID:16668703

  14. Modeling electron competition among nitrogen oxides reduction and N2O accumulation in denitrification.

    PubMed

    Pan, Yuting; Ni, Bing-Jie; Yuan, Zhiguo

    2013-10-01

    Competition for electrons among different steps of denitrification has previously been shown to occur, and to play an important role in the accumulation and emission of N2O in wastewater treatment. However, this electron competition is not recognized in the current denitrification models, limiting their ability to predict N2O accumulation during denitrification. In this work, a new denitrification model is developed for wastewater treatment processes. It describes electron competition among the four steps of denitrification, through modeling the carbon oxidation and nitrogen reduction processes separately, in contrast to the existing models that directly couple these two types of processes. Electron carriers are introduced to link carbon oxidation, which donates electrons to carriers, and nitrogen oxides reduction, which receives electrons from these carriers. The relative ability of each denitrification step to compete for electrons is modeled through the use of different affinity constants with reduced carriers. Model calibration and validation results demonstrate that the developed model is able to reasonably describe the nitrate, nitrite, and N2O reduction rates of a methanol-utilizing denitrifying culture under various carbon and nitrogen oxides supplying conditions. The model proposed, while subject to further validation, is expected to enhance our ability to predict N2O accumulation in denitrification. PMID:24001217

  15. Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: kinetics and intermediates.

    PubMed

    Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

    2012-11-30

    C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC-MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N(2)-saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO(2) system by changing the reaction atmospheres. PMID:23046696

  16. A dinuclear copper(II) electrocatalyst both water reduction and oxidation

    NASA Astrophysics Data System (ADS)

    Zhou, Ling-Ling; Fang, Ting; Cao, Jie-Ping; Zhu, Zhi-Hong; Su, Xiao-Ting; Zhan, Shu-Zhong

    2015-01-01

    Splitting water is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for these reactions, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Until now, there is as yet no report on both water oxidation and reduction by identical catalyst. Reported here is the first soluble copper-based catalyst, Cu(Me2oxpn)Cu(OH)2] 1 (Me2oxpn: N,N‧-bis(2,2‧-dimethyl-3-aminopropyl)oxamido) for both electrolytic water oxidation and reduction. Water oxidation occurs at an overpotential of 636 mV vs SHE to give O2 with a turnover frequency (TOF) of ∼2.14 s-1. Electrochemical studies also indicate that 1 is a soluble molecular species, that is among the most rapid homogeneous water reduction catalysts, with a TOF of 654 mol of hydrogen per mole of catalyst per hour at an overpotential of 789 mV vs SHE (pH 7.0). Sustained water reduction catalysis occurs at glassy carbon (GC) to give H2 over a 32 h electrolysis period with 95% Faradaic yield and no observable decomposition of the catalyst.

  17. Sequential reductive and oxidative conditions used to biodegradation of organochlorine pesticides by native bacteria.

    NASA Astrophysics Data System (ADS)

    Kopytko, M.; Correa-Torres, S. N.; Plata, A.

    2016-07-01

    Despite restrictions and bans on the use of many organochlorine pesticides in the 1970s and 1980s, they continue to persist in the environment today. This is the case of Agustin Codazzi, Cesar where the organochlorine pesticides were buried without control in the soil in 1999, after being banned their use. Nowadays is necessary to find the best method, which allows remediation of this soils. Reductive dechlorination is the first and limiting step in the metabolism of many organochlorine pesticides by anaerobic bacteria. In this study the reductive conditions were enhanced by addition of biogas as an auxiliary electron donors.The soil sample was taken from the zone at Agustin Codazzi, Cesar, and their characteristics correspond to a loam soil with low nutrient and slight compaction. The experimental tests were performed by varying the exposure time of a reducer to oxidative environment. Reductive conditions were enhanced by methane from biogas and oxidative environment was generated by air blown to stimulate a metabolic process of the soil native bacteria. Removals between 70 and 78.9% of compounds such as 4,4'-DDT, 4, 4'-DDD, 4,4'-DDE, Endrin and Trans- Chlordane, detected by gas chromatography analysis, were achieved under reductive/oxidative conditions during 120 days. Furthermore, bacterial strains capable of degrading organochlorine pesticides were selected from the native bacteria, and identified by the purified and identified based on its morphological characteristics and 16S rDNA sequencing.

  18. Polydopamine-graphene oxide derived mesoporous carbon nanosheets for enhanced oxygen reduction

    NASA Astrophysics Data System (ADS)

    Qu, Konggang; Zheng, Yao; Dai, Sheng; Qiao, Shi Zhang

    2015-07-01

    Composite materials combining nitrogen-doped carbon (NC) with active species represent a paramount breakthrough as alternative catalysts to Pt for the oxygen reduction reaction (ORR) due to their competitive activity, low cost and excellent stability. In this paper, a simple strategy is presented to construct graphene oxide-polydopamine (GD) based carbon nanosheets. This approach does not need to modify graphene and use any catalyst for polymerization under ambient conditions, and the obtained carbon nanosheets possess adjustable thicknesses and uniform mesoporous structures without using any template. The thickness of GD hybrids and the carbonization temperature are found to play crucial roles in adjusting the microstructure of the resulting carbon nanosheets and, accordingly their ORR catalytic activity. The optimized carbon nanosheet generated by a GD hybrid of 5 nm thickness after 900 °C carbonization exhibits superior ORR activity with an onset potential of -0.07 V and a kinetic current density of 13.7 mA cm-2 at -0.6 V. The unique mesoporous structure, high surface areas, abundant defects and favorable nitrogen species are believed to significantly benefit the ORR catalytic process. Furthermore, it also shows remarkable durability and excellent methanol tolerance outperforming those of commercial Pt/C. In view of the physicochemical versatility and structural tunability of polydopamine (PDA) materials, our work would shed new light on the understanding and further development of PDA-based carbon materials for highly efficient electrocatalysts.Composite materials combining nitrogen-doped carbon (NC) with active species represent a paramount breakthrough as alternative catalysts to Pt for the oxygen reduction reaction (ORR) due to their competitive activity, low cost and excellent stability. In this paper, a simple strategy is presented to construct graphene oxide-polydopamine (GD) based carbon nanosheets. This approach does not need to modify graphene and use

  19. Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.; Mann, C.J.

    2000-03-01

    Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial Fe(III) content remained in the columns at the end of the experiment. The near-quantitative removal of Fe was visibly evidenced by extensive bleaching of color from the sand in the columns. In contrast to the column reactors, Fe(II) production quickly reached an asymptote in batch cultures, and only (13.0 {+-} 2.2)% (n = 3) of the Fe(III) oxide content was reduced. Sustained bacterial-cell growth occurred in the column reactors, leading to the production and export of a quantity of cells 100-fold greater than that added during inoculation. Indirect estimates of cell growth, based on the quantity of Fe(III) reduced, suggest that only an approximate doubling of initial cell abundance was likely to have occurred in the batch cultures. Their results indicate that removal of biogenic Fe(II) via aqueous-phase transport in the column reactors decreased the passivating influence of surface-bound Fe(II) on oxide reduction activity, thereby allowing a dramatic increase in the extent of Fe(III) oxide reduction and associated bacterial growth. These findings have important implications for understanding the fate of organic and inorganic contaminants whose geochemical behavior is linked to Fe(III) oxide reduction.

  20. Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation

    SciTech Connect

    Rakowski DuBois, Mary; DuBois, Daniel L.

    2009-12-15

    The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This review focuses on work from our laboratories on developing molecular electrocatalysts for CO2 reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO2 from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox active CO2 carriers for concentrating CO2. Catalysts for CO2 reduction to form CO have also been developed based on a [Pd(triphosphine)(solvent)]2+ platform. A required feature for catalytic activity is the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Participation of a second metal in CO2 binding also appears to be required for achieving very active catalysts as suggested by structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)]2+ units. Molecular electrocatalysts for H2 production and oxidation based on [Ni(diphosphine)2]2+ complexes are also described. These catalysts require the optimization of both first and second coordination spheres similar to that of the palladium CO2 reduction catalysts. In this case, structural features of the first coordination sphere can be used to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H2. The second coordination sphere can be used to incorporate pendant bases that assist in a number of important functions including H2 binding, H2 cleavage, and the

  1. Facilitated biological reduction of nitroaromatic compounds by reduced graphene oxide and the role of its surface characteristics

    PubMed Central

    Li, Lei; Liu, Qi; Wang, Yi-Xuan; Zhao, Han-Qing; He, Chuan-Shu; Yang, Hou-Yun; Gong, Li; Mu, Yang; Yu, Han-Qing

    2016-01-01

    How reduced graphene oxide (RGO) mediates the reductive transformation of nitroaromatic pollutants by mixed cultures and the role of its surface characteristics were evaluated in this study. Different electron donors were applied to investigate the interaction between RGO and anaerobic microbes. Moreover, the influence of the surface properties of RGO on biological nitroaromatic removal was further elucidated. The results show that RGO could achieve an approximate one-fold rate increase of nitrobenzene reduction by mixed culture with glucose as an electron donor. Selective elimination of oxygen moieties on the RGO surface, such as quinone groups, decreased the nitrobenzene transformation rate, whereas doping nitrogen into the RGO framework exhibited a positive effect. The study indicates that graphene-based carbon nanomaterials have the potential to accelerate the biological transformation of nitroaromatic compounds and that the functionalization of these carbon nanomaterials, especially through surface modification, would further enhance the conversion efficiency of contaminants. PMID:27439321

  2. Facilitated biological reduction of nitroaromatic compounds by reduced graphene oxide and the role of its surface characteristics.

    PubMed

    Li, Lei; Liu, Qi; Wang, Yi-Xuan; Zhao, Han-Qing; He, Chuan-Shu; Yang, Hou-Yun; Gong, Li; Mu, Yang; Yu, Han-Qing

    2016-01-01

    How reduced graphene oxide (RGO) mediates the reductive transformation of nitroaromatic pollutants by mixed cultures and the role of its surface characteristics were evaluated in this study. Different electron donors were applied to investigate the interaction between RGO and anaerobic microbes. Moreover, the influence of the surface properties of RGO on biological nitroaromatic removal was further elucidated. The results show that RGO could achieve an approximate one-fold rate increase of nitrobenzene reduction by mixed culture with glucose as an electron donor. Selective elimination of oxygen moieties on the RGO surface, such as quinone groups, decreased the nitrobenzene transformation rate, whereas doping nitrogen into the RGO framework exhibited a positive effect. The study indicates that graphene-based carbon nanomaterials have the potential to accelerate the biological transformation of nitroaromatic compounds and that the functionalization of these carbon nanomaterials, especially through surface modification, would further enhance the conversion efficiency of contaminants. PMID:27439321

  3. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    SciTech Connect

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.

  4. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    DOE PAGESBeta

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62).more » These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.« less

  5. Global Change Simulations Affect Potential Methane Oxidation in Upland Soils

    NASA Astrophysics Data System (ADS)

    Blankinship, J. C.; Hungate, B. A.

    2004-12-01

    Atmospheric concentrations of methane (CH4) are higher now than they have ever been during the past 420,000 years. However, concentrations have remained stable since 1999. Emissions associated with livestock husbandry are unlikely to have changed, so some combination of reduced production in wetlands, more efficient capture by landfills, or increased consumption by biological CH4 oxidation in upland soils may be responsible. Methane oxidizing bacteria are ubiquitous in upland soils and little is known about how these bacteria respond to anthropogenic global change, and how they will influence - or already are influencing - the radiative balance of the atmosphere. Might ongoing and future global changes increase biological CH4 oxidation? Soils were sampled from two field experiments to assess changes in rates of CH4 oxidation in response to global change simulations. Potential activities of CH4 oxidizing bacterial communities were measured through laboratory incubations under optimal temperature, soil moisture, and atmospheric CH4 concentrations (~18 ppm, or 10x ambient). The ongoing 6-year multifactorial Jasper Ridge Global Change Experiment (JRGCE) simulates warming, elevated precipitation, elevated atmospheric CO2, elevated atmospheric N deposition, and increased wildfire frequency in an annual grassland in a Mediterranean-type climate in central California. The ongoing 1-year multifactorial Merriam Climate Change Experiment (MCCE) simulates warming, elevated precipitation, and reduced precipitation in four different types of ecosystems along an elevational gradient in a semi-arid climate in northern Arizona. The high desert grassland, pinyon-juniper woodland, ponderosa pine forest, and mixed conifer forest ecosystems range in annual precipitation from 100 to 1000 mm yr-1, and from productivity being strongly water limited to strongly temperature limited. Among JRGCE soils, elevated atmospheric CO2 increased potential CH4 oxidation rates (p=0.052) and wildfire

  6. Synthesis and Characterization of Iodine laden Graphene Nano Platelets via reduction of Graphene Oxide Using Hydrogen Iodide

    NASA Astrophysics Data System (ADS)

    Sundararaj, Joe Livingston

    This research thesis proposes a novel method for the synthesis, analysis and characterization of Iodinated X-Ray contrast agents using Graphene Nanoplatelets (GNPs) for Computed Tomographic Imaging. Graphene Oxide was synthesized using the Hummers Method of Oxidation [1] through oxidative treatment of Graphite with Potassium Permanganate (KMnO4). The resulting Graphene Oxide was chemically reduced using varying concentrations of Hydrogen Iodide or Hydroiodic acid (HI), rather than the conventionally used highly toxic Hydrazine Hydrate (N2H4) to strip off the oxygen functionalities. In the process of chemical reduction using Hydrogen Iodide, we hypothesized that this would result in the incorporation of Iodine into the Graphitic structure. Raman Spectroscopy, EDS along with XRD analysis provided evidence for the reduction of GO. Raman spectra for reduced GNPs showed an increase in ID/IG ratio from that of graphene oxide and also a peak at 154cm-1 attributed to I5 -. EDS/EDX spectra for HI reduced GO showed a peak at X-ray energy level 3.94KeV characteristic of Iodine. Further analysis using Ion-Selective Electrode measurements confirmed the presence of about 10% Iodine in the Hydroiodic acid reduced samples. SEM and TEM images showed a brief morphology of the Graphene Nanoplatelets. Finally, to elucidate the possibility of Iodinated GNPs to be developed into potential CT contrast agents in the near or far future, CT Phantoms of Iodine loaded GNPs at a concentration of 40mg/ml in water showed excellent contrast density with water and dilute Hydroiodic acid as controls.

  7. Potential benefits of solar reflective car shells: cooler cabins, fuel savings and emission reductions

    SciTech Connect

    Levinson, Ronnen; Pan, Heng; Ban-Weiss, George; Rosado, Pablo; Paolini, Riccardo; Akbari, Hashem

    2011-05-11

    Abstract: Vehicle thermal loads and air conditioning ancillary loads are strongly influenced by the absorption of solar energy. The adoption of solar reflective coatings for opaque surfaces of the vehicle shell can decrease the ?soak? temperature of the air in the cabin of a vehicle parked in the sun, potentially reducing the vehicle?s ancillary load and improving its fuel economy by permitting the use of a smaller air conditioner. An experimental comparison of otherwise identical black and silver compact sedans indicated that increasing the solar reflectance (?) of the car?s shell by about 0.5 lowered the soak temperature of breath-level air by about 5?6?C. Thermal analysis predicts that the air conditioning capacity required to cool the cabin air in the silver car to 25?C within 30min is 13percent less than that required in the black car. Assuming that potential reductions in AC capacity and engine ancillary load scale linearly with increase in shell solar reflectance, ADVISOR simulations of the SC03 driving cycle indicate that substituting a typical cool-colored shell (?=0.35) for a black shell (?=0.05) would reduce fuel consumption by 0.12L per 100km (1.1percent), increasing fuel economy by 0.10kmL?1 [0.24mpg] (1.1percent). It would also decrease carbon dioxide (CO2) emissions by 2.7gkm?1 (1.1percent), nitrogen oxide (NOx) emissions by 5.4mgkm?1 (0.44percent), carbon monoxide (CO) emissions by 17mgkm?1 (0.43percent), and hydrocarbon (HC) emissions by 4.1mgkm?1 (0.37percent). Selecting a typical white or silver shell (?=0.60) instead of a black shell would lower fuel consumption by 0.21L per 100km (1.9percent), raising fuel economy by 0.19kmL?1 [0.44mpg] (2.0percent). It would also decrease CO2 emissions by 4.9gkm?1 (1.9percent), NOx emissions by 9.9mgkm?1 (0.80percent), CO emissions by 31mgkm?1 (0.79percent), and HC emissions by 7.4mgkm?1 (0.67percent). Our simulations may underestimate emission reductions because emissions in standardized driving cycles are

  8. Potential of front-face fluorescence to monitor OM reduction in drinking water during potabilization process

    NASA Astrophysics Data System (ADS)

    Lacotte, Pierre

    2014-05-01

    Elimination of OM in drinking water represents a great challenge for municipalities and technical actors to ensure that it can be safely used for consumption purposes. Indeed, current indicators such as Total Organic Carbon (TOC), turbidity or UV-Absorbance at 254 nm (UVA254) enable only non-specific overview of the amount of organic residuals in water. Fluorescence EEMs are a potent tool for discrimination and deep analysis of OM detailed composition and behaviour. It has been shown that several forms of OM co-exist in raw water, and come from various origins (bacteria, humic compounds…). Potabilization operation is composed of different steps that aim at decreasing all forms of OM using chemical as well as physical methods (ozone oxidation, filtration on activated carbon or sand, flocculation etc.). Unfortunately, it has been observed that reduction of OM during this process was not identical for all the forms, and the process showed a particular lack of efficiency during raining periods. 130 samples of water at various stages of potabilization were analyzed using home-made compact fluorometer, an apparatus composed of UV excitation LEDs. Using chemometrical treatment of spectral data, we put into highlight 5 different forms of OM that were identified according to litterature data. We evidenced the critical steps of the purification on OM reduction, as well as the relative content of each form from raw to product water. In particular, we showed that two forms were less reduced than the other three, so that progressive enrichment of total OM in the former was observed throughout the process. Moreover, a study was carried out in order to establish calibration models over conventional analyses using the spectral information. Highly satisfying models were thus obtained over TOC, turbidity and UVA254, with average RMSEC values of 13%, 7% and 16% respectively. These results demonstrate the potential of the fluorescence analyzer to simultaneously predict three major

  9. Climate change reduces warming potential of nitrous oxide by an enhanced Brewer-Dobson circulation

    NASA Astrophysics Data System (ADS)

    Kracher, Daniela; Reick, Christian H.; Manzini, Elisa; Schultz, Martin G.; Stein, Olaf

    2016-06-01

    The Brewer-Dobson circulation (BDC), which is an important driver of the stratosphere-troposphere exchange, is expected to accelerate with climate change. One particular consequence of this acceleration is the enhanced transport of nitrous oxide (N2O) from its sources at the Earth's surface toward its main sink region in the stratosphere, thus inducing a reduction in its lifetime. N2O is a potent greenhouse gas and the most relevant currently emitted ozone-depleting substance. Here we examine the implications of a reduced N2O lifetime in the context of climate change. We find a decrease in its global warming potential (GWP) and, due to a decline in the atmospheric N2O burden, also a reduction in its total radiative forcing. From the idealized transient global warming simulation we can identify linear regressions for N2O sink, lifetime, and GWP with temperature rise. Our findings are thus not restricted to a particular scenario.

  10. Nitrate Reduction to Nitrite, a Possible Source of Nitrite for Growth of Nitrite-Oxidizing Bacteria

    PubMed Central

    Belser, L. W.

    1977-01-01

    Growth yields and other parameters characterizing the kinetics of growth of nitrite-oxidizing bacteria are presented. These parameters were measured during laboratory enrichments of soil samples with added nitrite. They were then used to reanalyze data for nitrite oxidizer growth in a previously reported field study (M. G. Volz, L. W. Belser, M. S. Ardakani, and A. D. McLaren, J. Environ. Qual. 4:179-182, 1975), where nitrate, but not nitrite or ammonium, was added. In that report, analysis of the field data indicated that in unsaturated soils, the reduction of nitrate to nitrite may be a significant source of nitrite for the growth of nitrite oxidizers. A yield of 1.23 × 104 cells per μg of N was determined to be most appropriate for application to the field. It was determined that if nitrite came only from mineralized organic nitrogen via ammonium oxidation, 35 to 90% of the organic nitrogen would have had to have been mineralized to produce the growth observed. However, it is estimated that only about 2% of the organic nitrogen could have been mineralized during the growth period. Thus, it appears that another source of nitrite is required, the most likely being the reduction of nitrate to nitrite coupled to the oxidation of organic matter. PMID:921264

  11. IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

    SciTech Connect

    Jantzen, C.; Johnson, F.

    2012-06-05

    During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, the acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.

  12. A potential biomarker for fatigue: Oxidative stress and anti-oxidative activity.

    PubMed

    Fukuda, Sanae; Nojima, Junzo; Motoki, Yukari; Yamaguti, Kouzi; Nakatomi, Yasuhito; Okawa, Naoko; Fujiwara, Kazumi; Watanabe, Yasuyoshi; Kuratsune, Hirohiko

    2016-07-01

    We sought to determine whether oxidative stress and anti-oxidative activity could act as biomarkers that discriminate patients with chronic fatigue syndrome (CFS) from healthy volunteers at acute and sub-acute fatigue and resting conditions. We calculated the oxidative stress index (OSI) from reactive oxygen metabolites-derived compounds (d-ROMs) and the biological antioxidant potential (BAP). We determined changes in d-ROMs, BAP, and OSI in acute and sub-acute fatigue in two healthy groups, and compared their values at rest between patients with CFS (diagnosed by Fukuda 1994 criteria) and another group of healthy controls. Following acute fatigue in healthy controls, d-ROMs and OSI increased, and BAP decreased. Although d-ROMs and OSI were significantly higher after sub-acute fatigue, BAP did not decrease. Resting condition yielded higher d-ROMs, higher OSI, and lower BAP in patients with CFS than in healthy volunteers, but lower d-ROMs and OSI when compared with sub-acute controls. BAP values did not significantly differ between patients with CFS and controls in the sub-acute condition. However, values were significantly higher than in the resting condition for controls. Thus, measured of oxidative stress (d-ROMS) and anti-oxidative activity (BAP) might be useful for discriminating acute, sub-acute, and resting fatigue in healthy people from patients with CFS, or for evaluating fatigue levels in healthy people. PMID:27224647

  13. Novel Process for Solid State Reduction of Metal Oxides and Hydroxides

    NASA Astrophysics Data System (ADS)

    Luhrs, Claudia; Kane, Margaret; Leseman, Zayd; Phillips, Jonathan

    2013-02-01

    Recently the reductive expansion synthesis (RES) method was introduced as a means to create nano- and sub-micron metal particles and alloys by rapid heating of physical mixtures of urea with a metal nitrate. In the present work the generality of the RES method was demonstrated by creating metal micron and sub-micron particles from oxide and hydroxide precursors, and outlining the impact of temperature, precursor ratio, and gas flow rate on the product. For example, precursor selection impacted the temperature required for complete reduction, the amount of carbon present, and the size of the metal particles. For complete NiO reduction to micron scale particles, high urea content and a high temperature [ ca. 1073 K (800 °C)] were required. In contrast, Ni(OH)2 was reduced to metal at far lower temperatures. Moreover, the Ni particles formed from NiOH were sub-micron ( ca. 200 nm) in size and carbon encapsulated. Other parameter variations had a similarly significant impact. Indeed, the reciprocal relationship between inert gas flow rate and the extent of reduction supports the supposition that the primary mechanism of reduced metal particle formation is the reduction of metal oxide particles by gases produced by urea decomposition. Collectively these and other findings indicate the RES method can be manipulated to create a range of micron and sub-micron reduced metal particle architectures appropriate for different applications.

  14. A kinetic model for bacterial Fe(III) oxide reduction in batch cultures

    NASA Astrophysics Data System (ADS)

    Hacherl, Eric L.; Kosson, David S.; Cowan, Robert M.

    2003-04-01

    A model has been developed describing the microbial reduction of solid-phase electron acceptors (Fe(III) oxides) as well as dissolved electron acceptors (chelated Fe(III) or organic electron shuttles) in Shewanella alga BrY. The model utilized a multiple-substrate, Monod kinetics formulation. The Monod description of solid Fe(III) reduction requires a normalization of surface Fe concentration to biomass concentration in order to describe the "bioavailable" Fe(III) concentration. The model also contains provisions for irreversible sorption of Fe(II) to Fe(III) oxide surfaces and for the precipitation of Fe(III) carbonates. The loss of bioavailable Fe(III) due to sorption of Fe(II) was found to be minor, even for highly sorptive amorphous Fe(III) oxyhydroxides. However, the final extent of microbial reduction is very sensitive to the rate of siderite precipitation, assuming that siderite precipitation could partially occlude Fe(III) surface sites. The use of a multisubstrate Monod kinetics model enabled an evaluation of the effects of electron shuttles on solid Fe(III) reduction. Because the electron shuttle is recycled, very small additions can greatly increase the overall rate of solid Fe(III) reduction.

  15. Nitrogen oxides reduction by carbonaceous materials and carbon dioxide separation using regenerative metal oxides from fossil fuel based flue gas

    NASA Astrophysics Data System (ADS)

    Gupta, Himanshu

    The ever-growing energy demands due to rising global population and continuing lifestyle improvements has placed indispensable emphasis on fossil fuels. Combustion of fossil fuels leads to the emission of harmful gaseous pollutants such as oxides of sulfur (SOx) and nitrogen (NOx), carbon dioxide (CO2), mercury, particulate matter, etc. Documented evidence has proved that this air pollution leads to adverse environmental health. This dissertation focuses on the development of technologies for the control of NOx and CO2 emissions. The first part of the thesis (Chapters 2--6) deals with the development of carbon based post combustion NOx reduction technology called CARBONOX process. High temperature combustion oxidizes both atmospheric nitrogen and organic nitrogen in coal to nitric oxide (NO). The reaction rate between graphite and NO is slow and requires high temperature (>900°C). The presence of metallic species in coal char catalyzes the reaction. The reaction temperature is lowered in the presence of oxygen to about 600--850°C. Chemical impregnation, specifically sodium compounds, further lowers the reaction temperature to 350--600°C. Activated high sodium lignite char (HSLC) provided the best performance for NO reduction. The requirement of char for NOx reduction is about 8--12 g carbon/g NO reduced in the presence of 2% oxygen in the inlet gas. The second part of this dissertation (chapter 7--8) focuses on the development of a reaction-based process for the separation of CO2 from combustion flue gas. Certain metal oxides react with CO2 forming metal carbonates under flue gas conditions. They can be calcined separately to yield CO2. Calcium oxide (CaO) has been identified as a viable metal oxide for the carbonation-calcination reaction (CCR) scheme. CaO synthesized from naturally occurring precursors (limestone and dolomite) attained 45--55% of their stoichiometric conversion due to the susceptibility of their microporous structure. High surface area

  16. Process for the catalytic reduction of nitrogen oxides in gaseous mixtures

    SciTech Connect

    Ginger, E.A.

    1981-05-19

    A process for the reductive removal of a nitrogen oxide from a gaseous stream, particularly a stream containing oxygen, water, sulfur dioxide, nitrogen oxide and nitrogen, by contacting the stream with ammonia in the presence of a mixture of two catalysts. The first catalyst comprises copper or a copper compound, preferably copper sulfate supported on a porous carrier material. The second catalyst is a combination of metals or compounds thereof, preferably sulfates of vanadium and iron or tungsten and iron, also dispersed on a porous carrier material.

  17. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

    PubMed Central

    2013-01-01

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

  18. Reduction in nitrogen oxides emission on TGME-464 boiler of IRU power plant (Estonia)

    NASA Astrophysics Data System (ADS)

    Roslyakov, P. V.; Ionkin, I. L.

    2015-01-01

    The possibility for realization of measures on a reduction in nitrogen oxides emission on a TGME-464 (plant no. 2) boiler of the IRU power plant (Tallinn, Estonia) is investigated. Low-cost techno-logical measures, namely, nonstoichiometric burning and burning with the moderate controlled chemical underburning, are proposed and experimentally tested. Recommendations on the implementation of low-emission modes of burning natural gas into mode diagrams of the boiler are given. Nitrogen oxides emissions are reduced to the required level as a result of the implementation of the proposed measures.

  19. Oxidation-reduction processes in ground water at Naval Weapons Industrial Reserve Plant, Dallas, Texas

    USGS Publications Warehouse

    Jones, S.A.; Braun, Christopher L.; Lee, Roger W.

    2003-01-01

    Concentrations of trichloroethene in ground water at the Naval Weapons Industrial Reserve Plant in Dallas, Texas, indicate three source areas of chlorinated solvents?building 1, building 6, and an off-site source west of the facility. The presence of daughter products of reductive dechlorination of trichloroethene, which were not used at the facility, south and southwest of the source areas are evidence that reductive dechlorination is occurring. In places south of the source areas, dissolved oxygen concentrations indicated that reduction of oxygen could be the dominant process, particularly south of building 6; but elevated dissolved oxygen concentrations south of building 6 might be caused by a leaking water or sewer pipe. The nitrite data indicate that denitrification is occurring in places; however, dissolved hydrogen concentrations indicate that iron reduction is the dominant process south of building 6. The distributions of ferrous iron indicate that iron reduction is occurring in places south-southwest of buildings 6 and 1; dissolved hydrogen concentrations generally support the interpretation that iron reduction is the dominant process in those places. The generally low concentrations of sulfide indicate that sulfate reduction is not a key process in most sampled areas, an interpretation that is supported by dissolved hydrogen concentrations. Ferrous iron and dissolved hydrogen concentrations indicate that ferric iron reduction is the primary oxidation-reduction process. Application of mean first-order decay rates in iron-reducing conditions for trichloroethene, dichloroethene, and vinyl chloride yielded half-lives for those solvents of 231, 347, and 2.67 days, respectively. Decay rates, and thus half-lives, at the facility are expected to be similar to those computed. A weighted scoring method to indicate sites where reductive dechlorination might be likely to occur indicated strong evidence for anaerobic biodegradation of chlorinated solvents at six sites

  20. Self-Supplied Nano-Fusing and Transferring Metal Nanostructures via Surface Oxide Reduction.

    PubMed

    Ahn, Jaeho; Seo, Ji-Won; Kim, Jong Yun; Lee, Jaemin; Cho, Changsoon; Kang, Juhoon; Choi, Sung-Yool; Lee, Jung-Yong

    2016-01-20

    Here, we demonstrate that chemical reduction of oxide layers on metal nanostructures fuses junctions at nanoscale to improve the opto-electrical performance, and to ensure environmental stability of the interconnected nanonetwork. In addition, the reducing reaction lowers the adhesion force between metal nanostructures and substrates, facilitating the detachment of them from substrates. Detached metal nanonetworks can be easily floated on water and transferred onto various substrates including hydrophobic, floppy, and curved surfaces. Utilizing the detached metal nanostructures, semitransparent organic photovoltaics is fabricated, presenting the applicability of proposed reduction treatment in the device applications. PMID:26700597

  1. Rate of the reduction of the iron oxides in red mud by hydrogen and converted gas

    NASA Astrophysics Data System (ADS)

    Teplov, O. A.; Lainer, Yu. A.

    2013-01-01

    The drying and gas reduction of the iron oxides in the red mud of bauxite processing are studied. It is shown that at most 25% of aluminum oxide are fixed by iron oxides in this red mud, and the other 75% are fixed by sodium aluminosilicates. A software package is developed to calculate the gas reduction of iron oxides, including those in mud. Small hematite samples fully transform into magnetite in hydrogen at a temperature below 300°C and a heating rate of 500 K/h, and complete reduction of magnetite to metallic iron takes place below 420°C. The densification of a thin red mud layer weakly affects the character and temperature range of magnetizing calcination, and the rate of reduction to iron decreases approximately twofold and reduction covers a high-temperature range (above 900°C). The substitution of a converted natural gas for hydrogen results in a certain delay in magnetite formation and an increase in the temperature of the end of reaction to 375°C. In the temperature range 450-550°C, the transformation of hematite into magnetite in red mud pellets 1 cm in diameter in a converted natural gas is 30-90 faster than the reduction of hematite to iron in hydrogen. The hematite-magnetite transformation rate in pellets is almost constant in the temperature range under study, and reduction occurs in a diffusion mode. At a temperature of ˜500°C, the reaction layer thickness of pellets in a shaft process is calculated to be ˜1 m at a converted-gas flow rate of 0.1 m3/(m2 s) and ˜2.5 m at a flow rate of 0.25 m3/(m2 s). The specific capacity of 1 m2 of the shaft cross section under these conditions is 240 and 600 t/day, respectively. The use of low-temperature gas reduction processes is promising for the development of an in situ optimum red mud utilization technology.

  2. Anion exchange membranes for electrochemical oxidation-reduction energy storage system

    NASA Technical Reports Server (NTRS)

    Odonnell, P. M.; Sheibley, D. W.; Gahn, R. F.

    1977-01-01

    Oxidation-reduction couples in concentrated solutions separated by appropriate ion selective membranes were considered as an attractive approach to bulk electrical energy storage. A key problem is the development of the membrane. Several promising types of anionic membranes are discussed which were developed and evaluated for redox energy storage systems. The copolymers of ethyleneglycoldimethacrylate with either 2-vinylpyridine or vinylbenzl chloride gave stable resistance values compared to the copolymer of vinylbenzlchloride and divinylbenzene which served as the baseline membrane. A polyvinylchloride film aminated with tetraethylenepentamine had a low resistance but a high ion transfer rate. A slurry coated vinylpyridine had the lowest ion transfer rate. All these membranes functioned well in laboratory cells at ambient temperatures with the acidic chloride oxidant/reductant system, Fe 3, Fe 2/Ti 3, Ti 4.

  3. Laser-assisted reduction of graphene oxide for paper based large area flexible electronics

    NASA Astrophysics Data System (ADS)

    Balliu, E.; Andersson, H.; Engholm, M.; Forsberg, S.; Olin, H.

    2016-03-01

    In this work we present a promising method for fabrication of conductive tracks on paper based substrates by laser assisted reduction of Graphene Oxide (GO). Printed electronics on paper based substrates is be coming more popular due to lower cost and recyclability. Fabrication of conductive tracks is of great importance where metal, carbon and polymer inks are commonly used. An emerging option is reduced graphene oxide (r-GO), which can be a good conductor. Here we have evaluated reduction of GO by using a 532 nm laser source, showing promising results with a decrease of sheet resistance from >100 M Ω/Sqr for unreduced GO down to 126 Ω/Sqr. without any observable damage to the paper substrates.

  4. Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

    SciTech Connect

    Bailey, James L.; Barnes, Laurel A.; Wiedmeyer, Stanley G.; Williamson, Mark A.; Willit, James L.

    2014-07-08

    An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies and an anode shroud for each of the anode assemblies. The anode shroud may be used to dilute, cool, and/or remove off-gas from the electrolytic oxide reduction system. The anode shroud may include a body portion having a tapered upper section that includes an apex. The body portion may have an inner wall that defines an off-gas collection cavity. A chimney structure may extend from the apex of the upper section and be connected to the off-gas collection cavity of the body portion. The chimney structure may include an inner tube within an outer tube. Accordingly, a sweep gas/cooling gas may be supplied down the annular space between the inner and outer tubes, while the off-gas may be removed through an exit path defined by the inner tube.

  5. Graphenothermal reduction synthesis of 'exfoliated graphene oxide/iron (II) oxide' composite for anode application in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Petnikota, Shaikshavali; Marka, Sandeep Kumar; Banerjee, Arkaprabha; Reddy, M. V.; Srikanth, V. V. S. S.; Chowdari, B. V. R.

    2015-10-01

    Graphenothermal Reduction process is used to obtain exfoliated graphene oxide (EG)/iron (II) oxide (FeO) composite prepared at 650 °C for 5 h in argon. Structural and compositional analyses of the sample confirm the formation of EG/FeO composite. This composite shows a reversible capacity of 857 mAh g-1 at a current rate of 50 mA g-1 in the voltage range 0.005-3.0 V versus Li. An excellent capacity retention up to 60 cycles and high coulombic efficiency of 98% are also observed. Characteristic Fe2+/0 redox peaks observed in Cyclic Voltammetry measurement are explained in correlation with lithium storage mechanism. Thermal, electrical and impedance spectroscopy studies of EG/FeO composite are discussed in detail. Comparative electrochemical cycling studies of EG/FeO composite with Fe2O3 and Fe3O4 materials prepared under controlled conditions are also discussed.

  6. DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtlu

    2001-09-01

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments

  7. The effect of oxidizing water on metallic restorations in the mouth: in vitro reduction behavior of oxidizing water.

    PubMed

    Nishida, T

    1997-03-01

    Mouth-rinsing with oxydized water which contains electrolytically generated chlorine is known to hinder dental plaque formation and growth, but it also accelerates the deterioration of metallic restorations in the mouth. The present work consists of an in vitro study to elucidate the electrochemical reactions involved in the reduction of oxydized water on dental alloys through a systematic investigation of the potentiostatic polarization behavior of dental alloy electrodes. The five dental alloys selected for investigation were gold alloy, gold alloy containing platinum, silver-palladium-gold alloy, conventional amalgam and high copper amalgam. The corrosion potentials of all dental alloy electrodes were shown to be more noble in oxydized water than in 0.1N sodium chloride solution. The potential differences between the corrosion potentials were relatively small in the case of amalgam electrodes. The polarization curves for all of the dental alloy electrodes in oxydized water revealed reduction currents of chlorine, hypochlorous acid, dissolved oxygen and oxonium ion. The reduction of chlorine and hypochlorous acid started at a more noble potential than that of dissolved oxygen. The dental alloys studied, except the amalgams, did not dissolve excessively at the corrosion potentials in oxydized water. PMID:9198335

  8. Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis.

    PubMed

    Sun, Bo; Reddy, Ettireddy P; Smirniotis, Panagiotis G

    2005-08-15

    Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light. PMID:16173589

  9. Nitrate Reduction to Nitrite, Nitric Oxide and Ammonia by Gut Bacteria under Physiological Conditions

    PubMed Central

    Tiso, Mauro; Schechter, Alan N.

    2015-01-01

    The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome

  10. Nitrate reduction to nitrite, nitric oxide and ammonia by gut bacteria under physiological conditions.

    PubMed

    Tiso, Mauro; Schechter, Alan N

    2015-01-01

    The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome

  11. Nitrous oxide reduction in nodules: denitrification or N/sub 2/ fixation

    SciTech Connect

    Coyne, M.S.; Focht, D.D.

    1987-05-01

    Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor/sup +/) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor/sup -/) rhizobium strain (32H1) were incubated with 1% /sup 15/N/sub 2/O (95 atom% /sup 15/N) in the following three atmospheres: aerobic with C/sub 2/H/sub 2/ (10%), aerobic without C/sub 2/H/sub 2/, and anaerobic (argon atmosphere) without C/sub 2/H/sub 2/. The greatest production of /sup 15/N/sub 2/ occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more /sup 15/N/sub 2/ was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N/sub 2/O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase.

  12. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

    PubMed

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-08-15

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 μM for methane and 8.7 ± 1.5 μM for nitrite. PMID:26048927

  13. Green Approach for the Effective Reduction of Graphene Oxide Using Salvadora persica L. Root (Miswak) Extract

    NASA Astrophysics Data System (ADS)

    Khan, Mujeeb; Al-Marri, Abdulhadi H.; Khan, Merajuddin; Shaik, Mohammed Rafi; Mohri, Nils; Adil, Syed Farooq; Kuniyil, Mufsir; Alkhathlan, Hamad Z.; Al-Warthan, Abdulrahman; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H.

    2015-07-01

    Recently, green reduction of graphene oxide (GRO) using various natural materials, including plant extracts, has drawn significant attention among the scientific community. These methods are sustainable, low cost, and are more environmentally friendly than other standard methods of reduction. Herein, we report a facile and eco-friendly method for the bioreduction of GRO using Salvadora persica L. ( S. persica L.) roots (miswak) extract as a bioreductant. The as-prepared highly reduced graphene oxide (SP-HRG) was characterized using powder X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron (XPS) spectroscopy, and transmission electron microscopy (TEM). Various results have confirmed that the biomolecules present in the root extract of miswak not only act as a bioreductant but also functionalize the surface of SP-HRG by acting as a capping ligand to stabilize it in water and other solvents. The dispersion quality of SP-HRG in deionized water was investigated in detail by preparing different samples of SP-HRG with increasing concentration of root extract. Furthermore, the dispersibility of SP-HRG was also compared with chemically reduced graphene oxide (CRG). The developed eco-friendly method for the reduction of GRO could provide a better substitute for a large-scale production of dispersant-free graphene and graphene-based materials for various applications in both technological and biological fields such as electronics, nanomedicine, and bionic materials.

  14. Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process

    SciTech Connect

    Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young

    2012-11-15

    The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

  15. Green Approach for the Effective Reduction of Graphene Oxide Using Salvadora persica L. Root (Miswak) Extract.

    PubMed

    Khan, Mujeeb; Al-Marri, Abdulhadi H; Khan, Merajuddin; Shaik, Mohammed Rafi; Mohri, Nils; Adil, Syed Farooq; Kuniyil, Mufsir; Alkhathlan, Hamad Z; Al-Warthan, Abdulrahman; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2015-12-01

    Recently, green reduction of graphene oxide (GRO) using various natural materials, including plant extracts, has drawn significant attention among the scientific community. These methods are sustainable, low cost, and are more environmentally friendly than other standard methods of reduction. Herein, we report a facile and eco-friendly method for the bioreduction of GRO using Salvadora persica L. (S. persica L.) roots (miswak) extract as a bioreductant. The as-prepared highly reduced graphene oxide (SP-HRG) was characterized using powder X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron (XPS) spectroscopy, and transmission electron microscopy (TEM). Various results have confirmed that the biomolecules present in the root extract of miswak not only act as a bioreductant but also functionalize the surface of SP-HRG by acting as a capping ligand to stabilize it in water and other solvents. The dispersion quality of SP-HRG in deionized water was investigated in detail by preparing different samples of SP-HRG with increasing concentration of root extract. Furthermore, the dispersibility of SP-HRG was also compared with chemically reduced graphene oxide (CRG). The developed eco-friendly method for the reduction of GRO could provide a better substitute for a large-scale production of dispersant-free graphene and graphene-based materials for various applications in both technological and biological fields such as electronics, nanomedicine, and bionic materials. PMID:26138452

  16. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria

    PubMed Central

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua

    2015-01-01

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 μM for methane and 8.7 ± 1.5 μM for nitrite. PMID:26048927

  17. Kinetics of the reduction of the zinc oxide in zinc ferrite with iron

    SciTech Connect

    Donald, J.R.; Pickles, C.A.

    1995-12-31

    Electric arc furnace (EAF) dust, which can be considered as a by-product of the steel recycling process, contains significant quantities of recoverable zinc and iron, as well as hazardous elements such as cadmium, lead and chromium, which can be leached by ground water. The zinc in the EAF dust is found almost entirely in the form of either zinc oxide or zinc ferrite, the latter accounting for 20 to 50 percent of the total zinc. It is important that an efficient process be developed which renders the dust inert, while reclaiming the valuable metals to off-set processing costs. During the conventional carbothermic reduction processes, iron is formed, and this iron can participate in the reduction of the zinc oxide in zinc ferrite. In the present work, the reduction of the zinc oxide in zinc ferrite by iron according to the following reaction: ZnO{sup {sm_bullet}}Fe{sub 2}O{sub (s.s.)} + 2 Fe{sub (s)} = Zn{sub (g)} + 4 FeO{sub (s)} was studied in an argon atmosphere using a thermogravimetric technique. First, a thermodynamic analysis was performed using the F*A*C*T computational system. Then, the effects of briquette aspect ratio (l/d), temperature, zinc ferrite particle size, amount of iron added, as well as additions such as lime, sodium chloride, and calcium fluoride were investigated.

  18. Redox reactions in mammalian spermatogenesis and the potential targets of reactive oxygen species under oxidative stress

    PubMed Central

    Fujii, Junichi; Imai, Hirotaka

    2014-01-01

    Reduction-oxidation (Redox) reactions are ubiquitous mechanisms for vital activities in all organisms, and they play pivotal roles in the regulation of spermatogenesis as well. Here we focus on 3 redox-involved processes that have drawn much recent attention: the regulation of signal transduction by reactive oxygen species (ROS) such as hydrogen peroxide, oxidative protein folding in the endoplasmic reticulum (ER), and sulfoxidation of protamines during sperm chromatin condensation. The first 2 of these processes are emerging topics in cell biology and are applicable to most living cells, which includes spermatogenic cells. The roles of ROS in signal transduction have been elucidated in the last 2 decades and have received broad attention, most notably from the viewpoint of the proper control of mitotic signals. Redox processes in the ER are important because this is the organelle where secretory and membrane proteins are synthesized and proceed toward their functional structure, so that malfunction of the ER affects not only the involved cells but also the accepting cells of the secreted proteins in multicellular organisms. Sulfoxidation is the third of these processes, and the sulfoxidation of chromatin is a unique process in sperm maturation. During recent sulfoxidase research, GPX4 has emerged as a promising enzyme that plays essential roles in the production of fertile sperm, but the involvement of other redox proteins is also becoming evident. Because the molecules involved in the redox reactions are prone to oxidation, they can be sensitive to oxidative damage, which makes them potential targets for antioxidant therapy. PMID:26413390

  19. Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: I. Thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Sinder, M.; Burshtein, Z.; Pelleg, J.

    2014-04-01

    We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. We provide thermodynamic equilibrium analyses, yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons as functions of the ambient oxygen pressure. The results suggest that experimental study of different species concentrations at thermodynamic equilibrium as functions of pressure and temperature should allow assessment of various reversible reaction constants controlling the process. In the Part II companion paper, the kinetic (diffusion) characteristics are considered in detail.

  20. Reduction of etched AlGaAs sidewall roughness by oxygen-enhanced wet thermal oxidation

    NASA Astrophysics Data System (ADS)

    Liang, D.; Hall, D. C.

    2007-08-01

    The authors demonstrate that the oxidation smoothing of sidewall roughness of dry-etched Al0.3Ga0.7As ridge structures is enabled through a modified wet thermal oxidation process which involves the addition of dilute amounts of O2 to the water vapor ambient. High magnification cross-section and top-view scanning electron microscope imagings both before and after oxide removal clearly show a substantial reduction of photolithography- and dry-etching-induced sidewall roughness (from σ ˜100nm down to σ ˜1-2nm), occurring only with the participation of added O2. The smoothing process provides means to realize high-index-contrast GaAs-based optical waveguides with both low bend and scattering losses.

  1. Infrared observation of thermally activated oxide reduction within Al/SiOx/Si tunnel diodes

    NASA Astrophysics Data System (ADS)

    Brendel, R.; Hezel, R.

    1992-05-01

    Electron-beam-evaporated aluminum/silicon oxide/silicon tunnel diodes with an initial oxide thickness of 1.3 nm have been annealed for up to 1 h at temperatures from 213 to 369 °C. They have been investigated by infrared grazing internal reflection (GIR) spectroscopy and current-voltage measurements. The measured IR spectra were analyzed by computer modeling. All spectral features could be explained self-consistently within a Al/AlOy/SiOx/Si layer model. In the as-deposited state less than 0.6 monolayers of Al—O bonds are formed at the Al/SiOx interface. A thermally activated reduction of the ultrathin oxide film by Al was observed. The changes in the current-voltage curves induced by slight annealing (1 min at 213 °C) are accompanied by changes in the insulator-bonding structure, which GIR is sensitive enough to detect.

  2. Pilot-scale equipment development for lithium-based reduction of spent oxide fuel.

    SciTech Connect

    Herrmann, S. D.

    1998-04-24

    An integral function of the electrometallurgical conditioning of DOE spent nuclear fuel is the standardization of waste forms. Argonne National Laboratory (ANL) has developed and is presently demonstrating the electrometallurgical conditioning of sodium-bonded metal fuel from Experimental Breeder Reactor II, resulting in uranium, ceramic waste, and metal waste forms. Engineering studies are underway at ANL in support of pilot-scale equipment development, which would precondition irradiated oxide fuel and likewise demonstrate the application of electrometallurgical conditioning to such non-metallic fuels. This paper highlights the integration of proposed spent oxide fuel conditioning with existing electrometallurgical processes. Additionally, technical bases for engineering activities to support a scale up of an oxide reduction process are described.

  3. Nitric oxide reduction in BioDeNOx reactors: kinetics and mechanism.

    PubMed

    van der Maas, Peter; Manconi, Isabella; Klapwijk, Bram; Lens, Piet

    2008-08-15

    Biological reduction of nitric oxide (NO) to di-nitrogen (N(2)) gas in aqueous Fe(II)EDTA(2-) solutions is a key reaction in BioDeNOx, a novel process for NOx removal from flue gases. The mechanism and kinetics of the first step of NO reduction, that is, the conversion of NO to N(2)O, was determined in batch experiments using various types of inocula. Experiments were performed in Fe(II)EDTA(2-) medium (5-25 mM) under BioDeNOx reactor conditions (55 degrees C, pH 7.2 +/- 0.2) with ethanol as external electron donor. BioDeNOx reactor mixed liquor gave the highest NO reduction rates (+/-0.34 nmol s(-1) mg(prot)(-1)) with an estimated K(m) value for NO lower than 10 nM. The specific NO (to N(2)O) reduction rate depended on the NO (aq) and Fe(II)EDTA(2-) concentration as well as the temperature. The experimental results, complemented with kinetic and thermodynamic considerations, show that Fe(II)EDTA(2-), and not ethanol, is the primary electron donor for NO reduction, that is, the BioDeNOx reactor medium (the redox system Fe(II)EDTA(2-)/Fe(III)EDTA(-)) interferes with the NO reduction electron transfer chain and thus enhances the NO denitrification rate. PMID:18553393

  4. Potential of Reduction in CO2 Emission by Biomass Power Generation with Thinning Residues

    NASA Astrophysics Data System (ADS)

    Makino, Yosuke; Kato, Takeyoshi; Suzuoki, Yasuo

    In Japan, forest thinning residues as woody biomass have potential to increase domestic primary energy supply, because there still remain many conifer plantations where thinning is not carried out. However, taking the reduction in carbon stock in forests into account, the additional thinning for energy supply may not contribute to the reduction in CO2 emission. Considering the change in the carbon stock in forests, this paper discusses the potential of reduction in CO2 emission by biomass power generation with thinning residues. As power generation systems with thinning residues, co-firing with coal in a utility's power station and a molten carbonate fuel cell (MCFC) with gasification system are taken into account. The results suggest that the co-firing of woody biomass supplied by the additional thinning at utilities' coal-fired power stations has a potential for reducing overall CO2 emission.

  5. Synthesis of high-performance graphene nanosheets by thermal reduction of graphene oxide

    SciTech Connect

    Wei, Ang; Wang, Jingxia; Long, Qing; Liu, Xiangmei; Li, Xingao; Dong, Xiaochen; Huang, Wei

    2011-11-15

    Graphical abstract: High-performance graphene nanosheets were synthesized by thermal reduction of graphene oxide under ethanol atmosphere. X-ray photoelectron spectroscopy, Raman spectroscopy and electrical transport measurements indicate that the resulting graphene nanosheets can effectively restore its graphic structure in GO and present high mobility. Highlights: {yields} Graphene nanosheets were synthesized by reduction of GO under ethanol atmosphere. {yields} Raman and XPS results indicate the reduced graphene sheets have high-performance. {yields} Graphene sheets field-effect transistors present high mobility. -- Abstract: High-performance graphene nanosheets have been synthesized by thermal reduction of graphene oxide (GO) under ethanol atmosphere. The reduced GO nanosheets were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy and electrical transport measurements, respectively. The results indicated that the thermal reduction of GO under ethanol atmosphere can effectively remove the oxygen-containing functional groups and restore its graphic structure compared to the ones obtained using hydrazine or hydrogen. The electrical measurements indicated that the electrical mobility of single-layer graphene sheet reduced under ethanol atmosphere at 900 {sup o}C can reach 29.08 cm{sup 2} V{sup -1} S{sup -1}.

  6. Scalable solid-template reduction for designed reduced graphene oxide architectures.

    PubMed

    Chen, Jun; Shepherd, Roderick L; Razal, Joselito M; Huang, Xiao; Zhang, Weimin; Zhao, Jie; Harris, Andrew T; Wang, Shu; Minett, Andrew I; Zhang, Hua

    2013-08-28

    Herein, we report a solid-state reduction process (in contrast to solution-based approach) by using an environmentally friendly reductant, such as vitamin C (denoted VC), to be directly employed to solid-state graphene oxide (GO) templates to give the highly active rGO architecture with a sheet resistance of as low as 10 Ω sq(-1). In addition, predesigned rGO patterns/tracks with tunable resistivity can be directly "written" on a preprepared solid GO film via the inkjet-printing technique using VC/H2O as the printing-ink. This advanced reduction process allows foreign active materials to be preincorporated into the GO matrix to form quality active composite architectures. PMID:23790146

  7. The use of coal in a solid phase reduction of iron oxide

    NASA Astrophysics Data System (ADS)

    Nokhrina, O. I.; Rozhihina, I. D.; Hodosov, I. E.

    2015-09-01

    The results of the research process of producing metalized products by solid-phase reduction of iron using solid carbonaceous reducing agents. Thermodynamic modeling was carried out on the model of the unit the Fe-C-O and system with iron ore and coal. As a result of modeling the thermodynamic boundary reducing, oxidizing, and transition areas and the value of the ratio of carbon and oxygen in the system. Simulation of real systems carried out with the gas phase obtained in the pyrolys of coal. The simulation results allow to determine the optimal cost of coal required for complete reduction of iron ore from a given composition. The kinetics of the processes of solid-phase reduction of iron using coal of various technological brands.

  8. Simulation of the reduction process of solid oxide fuel cell composite anode based on phase field method

    NASA Astrophysics Data System (ADS)

    Jiao, Zhenjun; Shikazono, Naoki

    2016-02-01

    It is known that the reduction process influences the initial performances and durability of nickel-yttria-stabilized zirconia composite anode of the solid oxide fuel cell. In the present study, the reduction process of nickel-yttria stabilized zirconia composite anode is simulated based on the phase field method. An three-dimensional reconstructed microstructure of nickel oxide-yttria stabilized zirconia composite obtained by focused ion beam-scanning electron microscopy is used as the initial microstructure for the simulation. Both reduction of nickel oxide and nickel sintering mechanisms are considered in the model. The reduction rates of nickel oxide at different interfaces are defined based on the literature data. Simulation results are qualitatively compared to the experimental anode microstructures with different reduction temperatures.

  9. Quinone reduction by Rhodothermus marinus succinate:menaquinone oxidoreductase is not stimulated by the membrane potential

    SciTech Connect

    Fernandes, Andreia S.; Konstantinov, Alexander A.; Teixeira, Miguel; Pereira, Manuela M. . E-mail: mpereira@itqb.unl.pt

    2005-05-06

    Succinate:quinone oxidoreductase (SQR), a di-haem enzyme purified from Rhodothermus marinus, reveals an HQNO-sensitive succinate:quinone oxidoreductase activity with several menaquinone analogues as electron acceptors that decreases with lowering the redox midpoint potential of the quinones. A turnover with the low-potential 2,3-dimethyl-1,4-naphthoquinone that is the closest analogue of menaquinone, although low, can be detected in liposome-reconstituted SQR. Reduction of the quinone is not stimulated by an imposed K{sup +}-diffusion membrane potential of a physiological sign (positive inside the vesicles). Nor does the imposed membrane potential increase the reduction level of the haems in R. marinus SQR poised with the succinate/fumarate redox couple. The data do not support a widely discussed hypothesis on the electrogenic transmembrane electron transfer from succinate to menaquinone catalysed by di-haem SQRs. The role of the membrane potential in regulation of the SQR activity is discussed.

  10. Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes.

    PubMed

    Zhang, Yingying; Zhuang, Yao; Geng, Jinju; Ren, Hongqiang; Xu, Ke; Ding, Lili

    2016-04-15

    This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe(2+)/H2O2) and UV/H2O2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H2O2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H2O2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe(2+)/H2O2 had a molar ratio of 0.1 and a H2O2 concentration of 0.01molL(-1) with a pH of 3.0 and reaction time of 2h, 2.58-3.79 logs of target genes were removed. Under the initial effluent pH condition (pH=7.0), the removal was 2.26-3.35 logs. For the UV/H2O2 process, when the pH was 3.5 with a H2O2 concentration of 0.01molL(-1) accompanied by 30min of UV irradiation, all ARGs could achieve a reduction of 2.8-3.5 logs, and 1.55-2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H2O2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe(2+)/H2O2 molar ratios, H2O2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. PMID:26815295

  11. Probing the oxidation reduction properties of terrestrially and microbially derived dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Fimmen, Ryan L.; Cory, Rose M.; Chin, Yu-Ping; Trouts, Tamara D.; McKnight, Diane M.

    2007-06-01

    Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by 13C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of p Ka values.

  12. Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.

    PubMed

    Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi

    2015-01-01

    Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in

  13. DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS

    SciTech Connect

    Dr. Ates Akyurlu; Dr. Jale F. Akyurtlu

    2003-01-28

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with methane. Since the replacement of ammonia by methane is commercially very attractive, in this project, it was planned to investigate the effect of promoters on the activity and selectivity of copper oxide/cerium oxide-based catalysts and to obtain data on the reaction mechanism for the SCR with methane. The investigation of the reaction mechanism will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations. The last component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments indicated that manganese is a more effective promoter than rhodium on the supported copper oxide-ceria catalysts under study; the effectiveness of the promoter increases with the increase in Ce/Cu ratio. The TPD profiles of the unpromoted catalyst (Cu/Ce=3) is different than those promoted with 0.1% rhodium. In the current reporting period, the screening of the promoted catalysts were completed, sufficient amount of the selected catalysts were prepared and delivered to TDA for long term deactivation testing.

  14. Influence of sediment components on the immobilization of Zn during microbial Fe-(hydr)oxide reduction.

    PubMed

    Coby, Aaron J; Picardal, Flynn W

    2006-06-15

    The fate of Zn and other sorbed heavy metals during microbial reduction of iron oxides is different when comparing synthetic Fe-(hydr)oxides and natural sediments undergoing a similar degree of iron reduction. Batch experiments with the iron-reducing organism Shewanella putrefaciens were conducted to examine the effects of an aqueous complexant (nitrilotriacetic acid or NTA), two solid-phase complexants (kaolinite and montmorillonite), an electron carrier (anthraquinone disulfonic acid or AQDS), and a humic acid on the speciation of Zn during microbial reduction of synthetic goethite. Compared to systems containing only goethite and Zn, microbial Fe(III) reduction in the presence of clay resulted in up to a 50% reduction in Zn immobilization (insoluble in a 2 h 0.5 M HCl extraction) without affecting Fe(II) production. NTA (3 mM) increased Fe(II) production 2-fold and resulted in recovery of nearly 75% of Zn in the aqueous fraction. AQDS (50 microM) resulted in a 12.5% decrease in Fe(II) production and a 44% reduction in Zn immobilization. Humic acid additions resulted in up to a 25% decrease in Fe(II) production and 51% decrease in Zn immobilization. The results suggest that all the components examined here as either complexing agents or electron shuttles reduce the degree of Zn immobilization by limiting the availability of Zn for incorporation into newly formed biogenic minerals. These results have implications for the remediation of heavy metals in a variety of natural sediments. PMID:16830547

  15. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    PubMed

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. PMID:26351175

  16. Noise and Fuel Burn Reduction Potential of an Innovative Subsonic Transport Configuration

    NASA Technical Reports Server (NTRS)

    Guo, Yueping; Nickol, Craig L.; Thomas, Russell H.

    2014-01-01

    A study is presented for the noise and fuel burn reduction potential of an innovative double deck concept aircraft with two three-shaft direct-drive turbofan engines. The engines are mounted from the fuselage so that the engine inlet is over the main wing. It is shown that such an aircraft can achieve a cumulative Effective Perceived Noise Level (EPNL) about 28 dB below the current aircraft noise regulations of Stage 4. The combination of high bypass ratio engines and advanced wing design with laminar flow control technologies provide fuel burn reduction and low noise levels simultaneously. For example, the fuselage mounted engine position provides more than 4 EPNLdB of noise reduction by shielding the inlet radiated noise. To identify the potential effect of noise reduction technologies on this concept, parametric studies are presented to reveal the system level benefits of various emerging noise reduction concepts, for both engine and airframe noise reduction. These concepts are discussed both individually to show their respective incremental noise reduction potential and collectively to assess their aggregate effects on the total noise. Through these concepts approximately about 8 dB of additional noise reduction is possible, bringing the cumulative noise level of this aircraft to 36 EPNLdB below Stage 4, if the entire suite of noise reduction technologies would mature to practical application. In a final step, an estimate is made for this same aircraft concept but with higher bypass ratio, geared, turbofan engines. With this geared turbofan propulsion system, the noise is estimated to reach as low as 40-42 dB below Stage 4 with a fuel burn reduction of 43-47% below the 2005 best-in-class aircraft baseline. While just short of the NASA N+2 goals of 42 dB and 50% fuel burn reduction, for a 2025 in service timeframe, this assessment shows that this innovative concept warrants refined study. Furthermore, this design appears to be a viable potential future passenger

  17. Reinterpretation of reduction potential measurements done by linear sweep voltammetry in silicate melts

    NASA Technical Reports Server (NTRS)

    Colson, R. O.; Haskin, L. A.; Keedy, C. R.

    1991-01-01

    The equilibrium concentrations of Ni between silicate melt and Pt were determined experimentally as a function of oxygen fugacity. The results demonstrate that metallic species derived in linear sweep voltammetry experiments in silicate melts are diffusing into Pt electrodes and not into the melt, as was concluded by previoius studies. This requires reinterpretation of previous linear sweep voltammetry results and recalculation and correction of reported reduction potentials. This paper reports these corrected reduction potentials. Also reported are the activity coefficients for Ni in synthetic basalt and diopsidic melts and for Co in diopsidic melt.

  18. Potentially toxic element release by fenton oxidation of sewage sludge.

    PubMed

    Andrews, J P; Asaadi, M; Clarke, B; Ouki, S

    2006-01-01

    The presence, in sewage sludge, of excess levels of the potentially toxic elements (PTE) copper, zinc, chromium, cadmium, nickel, lead and mercury, could impact on our ability to recycle these residues in the future. Far stricter limits on the levels of PTEs are likely in proposed legislation. A method involving the dosing of Fenton's reagent, a mixture of ferrous iron and hydrogen peroxide, under acidic conditions was evaluated for its potential to reduce metal levels. The [Fe]:[H2O2] (w/w) ratio was found to give a good indication of the percentage copper and zinc elution obtainable. Sites with no iron dosing as part of wastewater treatment required extra iron to be added in order to initiate the Fenton's reaction. A significant reduction, in excess of 70%, of the copper and zinc was eluted from both raw primary and activated sludge solid fractions. Cadmium and nickel could be reduced to below detection limits but elution of mercury, lead and chromium was less than 40%. The iron catalyst concentration was found to be a crucial parameter. This process has the potential to reduce the heavy metal content of the sludge and allow the recycling of sludge to continue in a sustainable manner. PMID:17087386

  19. Reductive nitrosylation of nickel(ii) complex by nitric oxide followed by nitrous oxide release.

    PubMed

    Ghosh, Somnath; Deka, Hemanta; Dangat, Yuvraj B; Saha, Soumen; Gogoi, Kuldeep; Vanka, Kumar; Mondal, Biplab

    2016-06-21

    Ni(ii) complex of ligand ( = bis(2-ethyl-4-methylimidazol-5-yl)methane) in methanol solution reacts with an equivalent amount of NO resulting in a corresponding Ni(i) complex. Adding further NO equivalent affords a Ni(i)-nitrosyl intermediate with the {NiNO}(10) configuration. This nitrosyl intermediate upon subsequent reaction with additional NO results in the release of N2O and formation of a Ni(ii)-nitrito complex. Crystallographic characterization of the nitrito complex revealed a symmetric η(2)-O,O-nitrito bonding to the metal ion. This study demonstrates the reductive nitrosylation of a Ni(ii) center followed by N2O release in the presence of excess NO. PMID:27230278

  20. Observations of Oxygen Ion Behavior in the Lithium-Based Electrolytic Reduction of Uranium Oxide

    SciTech Connect

    Steven D. Herrmann; Shelly X. Li; Brenda E. Serrano-Rodriguez

    2009-09-01

    Parametric studies were performed on a lithium-based electrolytic reduction process at bench-scale to investigate the behavior of oxygen ions in the reduction of uranium oxide for various electrochemical cell configurations. Specifically, a series of eight electrolytic reduction runs was performed in a common salt bath of LiCl – 1 wt% Li2O. The variable parameters included fuel basket containment material (i.e., stainless steel wire mesh and sintered stainless steel) and applied electrical charge (i.e., 75 – 150% of the theoretical charge for complete reduction of uranium oxide in a basket to uranium metal). Samples of the molten salt electrolyte were taken at regular intervals throughout each run and analyzed to produce a time plot of Li2O concentrations in the bulk salt over the course of the runs. Following each run, the fuel basket was sectioned and the fuel was removed. Samples of the fuel were analyzed for the extent of uranium oxide reduction to metal and for the concentration of salt constituents, i.e., LiCl and Li2O. Extents of uranium oxide reduction ranged from 43 – 70% in stainless steel wire mesh baskets and 8 – 33 % in sintered stainless steel baskets. The concentrations of Li2O in the salt phase of the fuel product from the stainless steel wire mesh baskets ranged from 6.2 – 9.2 wt%, while those for the sintered stainless steel baskets ranged from 26 – 46 wt%. Another series of tests was performed to investigate the dissolution of Li2O in LiCl at 650 °C across various cathode containment materials (i.e., stainless steel wire mesh, sintered stainless steel and porous magnesia) and configurations (i.e., stationary and rotating cylindrical baskets). Dissolution of identical loadings of Li2O particulate reached equilibrium within one hour for stationary stainless steel wire mesh baskets, while the same took several hours for sintered stainless steel and porous magnesia baskets. Rotation of an annular cylindrical basket of stainless steel

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  2. Oxidative dissolution potential of biogenic and abiogenic TcO{sub 2} in subsurface sediments.

    SciTech Connect

    Fredrickson, J. K.; Zachara, J. M.; Plymale, A. E.; Heald, S. M.; McKinley, J. P.; Kennedy, D. W.; Liu, C.; Nachimuthu, P.

    2009-04-01

    Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O{sub 4}{sup -}] and less mobile in the reduced form [Tc(IV)O{sub 2} {center_dot} nH{sub 2}O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO{sub 2}-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 {micro}m-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were

  3. Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

    PubMed

    Kim, Wooyul; McClure, Beth Anne; Edri, Eran; Frei, Heinz

    2016-06-01

    The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described. PMID:27121982

  4. Oxidation of diesel-generated volatile organic compounds in the selective catalytic reduction process

    SciTech Connect

    Koebel, M.; Elsener, M.

    1998-10-01

    The main part of the VOCs (volatile organic compounds) contained in diesel exhaust ({approx}80%) is oxidized to CO and CO{sub 2} over an SCR (selective catalytic reduction) catalyst. CO is the major product of this oxidation, representing about 50--70% of the formed products (CO + CO{sub 2}). This preferential formation of CO leads to a pronounced increase of CO emissions when an SCR process is added to a diesel engine. A small fraction of the VOCs is selectively oxidized to carboxylic acids over the SCR catalyst. This selectivity is due to the acidic properties of the catalyst causing the preferential desorption at the oxidation state of the acid. The main products of these oxidation reactions are the lower monocarboxylic acids and some dicarboxylic acids forming stable anhydrides, especially maleic and phthalic acid. The highest emissions of these acids are found at low temperatures; they decrease at higher temperatures. Formic acid is preferentially decomposed into carbon monoxide and water. It must therefore be assumed that the strong increase of CO mentioned above is due to a mechanism involving the thermal decomposition of formic acid formed from various primary VOCs.

  5. Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process

    DOEpatents

    Gardner, Timothy J.; Lott, Stephen E.; Lockwood, Steven J.; McLaughlin, Linda I.

    1998-01-01

    A catalytic material of activated hydrous metal oxide doped with platinum, palladium, or a combination of these, and optionally containing an alkali or alkaline earth metal, that is effective for NO.sub.X reduction in an oxidizing exhaust stream from a combustion process is disclosed. A device for reduction of nitrogen oxides in an exhaust stream, particularly an automotive exhaust stream, the device having a substrate coated with the activated noble-metal doped hydrous metal oxide of the invention is also provided.

  6. Delineating Climatic Regions Where Upland Soil Iron Reduction Is Potentially Important At The Ecosystem Scale

    NASA Astrophysics Data System (ADS)

    Thompson, A.; Hodges, C. A.; Chadwick, O.

    2015-12-01

    Microbial iron(III) reduction is often coupled to carbon mineralization, resulting in net CO2 efflux from the soil profile. Recent reports of iron reduction in upland ecosystems suggests this process is not limited to flooded soils and sediments. However, quantifying ecosystem-scale iron reduction rates is challenging because the intermittent anoxia (low-oxygen) that facilitates iron reduction varies spatially throughout the landscape. To approach this challenge, we have measured the soil iron reduction potential using localized passive redox sensors across four climate gradients ranging from <600 mm y-1 to >4000 mm y-1 rainfall on soils derived from Hawaiian basalt aged 0.3 to 4,100 ky. At each site we installed ten iron metal-rods with a uniform surface coating of Fe(III)-oxyhydroxide. The rods were pushed into the soil to a depth of 90 cm and left in place for 14 d. Extracted rods were washed and imaged to quantify the fraction of Fe(III)-oxyhydroxide coating that was dissolved. In addition, we have characterized the iron mineral composition from surface and sub-surface horizons at similar sites using Mössbauer spectroscopy. Our results suggest that when annual rainfall exceeds 1800 - 2000 mm y-1, iron reduction is a common feature within the soil profile, regardless of soil age. In addition, we find that the pedogenesis of iron minerals proceeds along distinct trajectories above and below this iron reduction threshold.

  7. Oxidative Homeostasis Regulates the Response to Reductive Endoplasmic Reticulum Stress through Translation Control.

    PubMed

    Maity, Shuvadeep; Rajkumar, Asher; Matai, Latika; Bhat, Ajay; Ghosh, Asmita; Agam, Ganesh; Kaur, Simarjot; Bhatt, Niraj R; Mukhopadhyay, Arnab; Sengupta, Shantanu; Chakraborty, Kausik

    2016-07-19

    Reductive stress leads to the loss of disulfide bond formation and induces the unfolded protein response of the endoplasmic reticulum (UPR(ER)), necessary to regain proteostasis in the compartment. Here we show that peroxide accumulation during reductive stress attenuates UPR(ER) amplitude by altering translation without any discernible effect on transcription. Through a comprehensive genetic screen in Saccharomyces cerevisiae, we identify modulators of reductive stress-induced UPR(ER) and demonstrate that oxidative quality control (OQC) genes modulate this cellular response in the presence of chronic but not acute reductive stress. Using a combination of microarray and relative quantitative proteomics, we uncover a non-canonical translation attenuation mechanism that acts in a bipartite manner to selectively downregulate highly expressed proteins, decoupling the cell's transcriptional and translational response during reductive ER stress. Finally, we demonstrate that PERK, a canonical translation attenuator in higher eukaryotes, helps in bypassing a ROS-dependent, non-canonical mode of translation attenuation. PMID:27373166

  8. Catalytic reduction of graphene oxide nanosheets by glutathione peroxidase mimetics reveals a new structural motif in graphene oxide.

    PubMed

    Vernekar, Amit A; Mugesh, Govindasamy

    2013-12-01

    A catalytic reduction of graphene oxide (GO) by glutathione peroxidase (GPx) mimics is reported. This study reveals that GO contains peroxide functionalities, in addition to the epoxy, hydroxyl and carboxylic acid groups that have been identified earlier. It also is shown that GO acts as a peroxide substrate in the GPx-like catalytic activity of organoselenium/tellurium compounds. The reaction of tellurol, generated from the corresponding ditelluride, reduces GO through the glutathione (GSH)-mediated cleavage of the peroxide linkage. The mechanism of GO reduction by the tellurol in the presence of GSH involves the formation of a tellurenic acid and tellurenyl sulfide intermediates. Interestingly, the GPx mimics also catalyze the decarboxylation of the carboxylic acid functionality in GO at ambient conditions. Whereas the selenium/tellurium-mediated catalytic reduction/decarboxylation of GO may find applications in bioremediation processes, this study suggests that the modification of GO by biologically relevant compounds such as redox proteins must be taken into account when using GO for biomedical applications because such modifications can alter the fundamental properties of GO. PMID:24281813

  9. Gadolinium oxide nanoparticles as potential multimodal imaging and therapeutic agents.

    PubMed

    Kim, Tae Jeong; Chae, Kwon Seok; Chang, Yongmin; Lee, Gang Ho

    2013-01-01

    Potentials of hydrophilic and biocompatible ligand coated gadolinium oxide nanoparticles as multimodal imaging agents, drug carriers, and therapeutic agents are reviewed. First of all, they can be used as advanced T1 magnetic resonance imaging (MRI) contrast agents because they have r1 larger than those of Gd(III)-chelates due to a high density of Gd(III) per nanoparticle. They can be further functionalized by conjugating other imaging agents such as fluorescent imaging (FI), X-ray computed tomography (CT), positron emission tomography (PET), and single photon emission tomography (SPECT) agents. They can be also useful for drug carriers through morphology modifications. They themselves are also potential CT and ultrasound imaging (USI) contrast and thermal neutron capture therapeutic (NCT) agents, which are superior to commercial iodine compounds, air-filled albumin microspheres, and boron ((10)B) compounds, respectively. They, when conjugated with targeting agents such as antibodies and peptides, will provide enhanced images and be also very useful for diagnosis and therapy of diseases (so called theragnosis). PMID:23432005

  10. Reduction Behavior of Iron Oxide in Semi-chacoal Composite Pellets

    NASA Astrophysics Data System (ADS)

    Konishi, Hirokazu; Fujimori, Shiro; Usui, Tateo

    Biomass has a novel advantage, i.e., no CO2 emissions, because of carbon neutral. We proposed semi-charcoal composite iron oxide pellets in order to decrease reducing agent at blast furnace and CO2 emissions. Japanese cedar were carbonized partly at maximum carbonization temperatures (TC, max = 823, 1073 and 1273 K) in order to obtain semi-charcoal with residual volatile matter (V.M.). It was found that the semi-charcoal retained much V.M., mainly H2, at TC, max = 823 K and that the semi-charcoal with some residual V.M. could be prepared by controlling TC, max in the carbonization. Composite pellets using such semi-charcoal have been prepared and reduced at reduction temperature (TR) in N2 gas atmosphere. Fractional reductions F(%) of the semi-charcoal composite pellets at TC, max = 823, 1073 and 1273 K were 17 ˜ 24 % for 60 min at TR = 1073 K. Moreover, fractional reduction F(%) of the semi-charcoal composite pellet at TC, max = 823 K was 62 % for 60 min at TR = 1173 K and was higher than the pellet at TC, max = 1273 K by about 30 %. When TC, max was lower, namely the pellet had more residual V.M., the reduction of iron oxide was more accelerated at TR = 1073 and 1173 K. Fractional reductions F(%) of all the semi-charcoal composite pellets were about 100 % for 50 ˜ 60 min at TR = 1273 K. These reducibility of semi-charcoal composite pellets were higher than those of semi-coal-char composite pellets at TR = 1273 K.

  11. Nitrate reduction coupled with pyrite oxidation in the surface sediments of a sulfide-rich ecosystem

    NASA Astrophysics Data System (ADS)

    Hayakawa, Atsushi; Hatakeyama, Mizuho; Asano, Ryoki; Ishikawa, Yuichi; Hidaka, Shin

    2013-06-01

    studies of denitrification have focused on organic carbon as an electron donor, but reduced sulfur can also support denitrification. Few studies have reported nitrate (NO3-) reduction coupled with pyrite oxidation and its stoichiometry in surface sediments, especially without experimental pyrite addition. In this study, we evaluated NO3- reduction coupled with sulfur oxidation by long-term incubation of surface sediments from a sulfide-rich ecosystem in Akita Prefecture, Japan. The surface sediments were sampled from a mud pool and a riverbed. Fresh sediments and water were incubated under anoxic conditions (and one oxic condition) at 20°C. NO3- addition increased the SO42- concentration and decreased the NO3- concentration. SO42- production (∆SO42-) was strongly and linearly correlated with NO3- consumption (∆NO3-) during the incubation period (R2 = 0.983, P < 0.01, and n = 8), and the slope of the regression (∆NO3-/∆SO42-) and the stoichiometry indicated sulfur-driven NO3- reduction by indigenous autotrophic denitrifying bacteria. Framboidal pyrite and marcasite (both FeS2) were present in the sediments and functioned as the electron donors for autotrophic denitrification. Both ∆NO3- and ∆SO42- were higher in the riverbed sediment than in the mud pool sediment, likely because of the higher amount of easily oxidizable S (pyrite) in the riverbed sediment. Consistently low ammonium (NH4+) concentrations indicated that NO3- reduction by dissimilatory NO3- reduction to NH4+ was small but could not be disregarded. Our results demonstrate that sulfide-rich ecosystems with easily oxidizable metal-bound sulfides such as FeS2 near the ground surface may act as denitrification hot spots.

  12. Electrocatalytic Activity of Transition Metal Oxide-Carbon Composites for Oxygen Reduction in Alkaline Batteries and Fuel Cells

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Jayachandrababu, KC; Kindler, A; Prakash, GKS; Narayanan, SR

    2013-06-07

    Conductive transition metal oxides (perovskites, spinels and pyrochlores) are attractive as catalysts for the air electrode in alkaline rechargeable metal-air batteries and fuel cells. We have found that conductive carbon materials when added to transition metal oxides such as calcium-doped lanthanum cobalt oxide, nickel cobalt oxide and calcium-doped lanthanum manganese cobalt oxide increase the electrocatalytic activity of the oxide for oxygen reduction by a factor of five to ten. We have studied rotating ring-disk electrodes coated with (a) various mass ratios of carbon and transition metal oxide, (b) different types of carbon additives and (c) different types of transition metal oxides. Our experiments and analysis establish that in such composite catalysts, carbon is the primary electro- catalyst for the two-electron electro-reduction of oxygen to hydroperoxide while the transition metal oxide decomposes the hydroperoxide to generate additional oxygen that enhances the observed current resulting in an apparent four-electron process. These findings are significant in that they change the way we interpret previous reports in the scientific literature on the electrocatalytic activity of various transition metal oxide- carbon composites for oxygen reduction, especially where carbon is assumed to be an additive that just enhances the electronic conductivity of the oxide catalyst. (C) 2013 The Electrochemical Society. All rights reserved.

  13. THEORETICAL INVESTIGATION INTO THE POTENTIAL OF HALOGENATED METHANES TO UNDERGO REDUCTIVE METABOLISM

    EPA Science Inventory

    The density-functional theory (DFT) based computational chemistry software package DMol was used to provide insight into the reductive potentials of a series of halomethanes. t is known that certain members of this series are readily reduced in vivo via catalysis by cytochrome P4...

  14. One-electron standard reduction potentials of nitroaromatic and cyclic nitramine explosives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Extensive studies have been conducted in the past decades to predict the environmental abiotic and biotic redox fate of nitroaromatic and nitramine explosives. However, surprisingly little information is available on one-electron standard reduction potentials (Eo(R-NO2/R-NO2_)). The Eo(R-NO2/R-NO2...

  15. Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

    SciTech Connect

    Caporuscio, F.A.; Vaniman, D.T.

    1985-04-01

    The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe{sup 3+}-bearing phases) exclusively. Estimates of Fe{sup 2+}-bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn{sup 4+}), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12

  16. Reduction of nitric oxide by ammonia at atmospheric pressures over platinum polycrystalline foils as model catalysts

    SciTech Connect

    Katona, T.; Guczi, L.; Somorjai, G.A.

    1991-12-01

    The reduction of nitric oxide with ammonia was studied using batch-mode and flow-mode measurements in partial pressure ranges of 70-660 Pa (0.5-5 Torr) on polycrystalline platinum foils over the temperature range of 373-633 K. The reaction products observed were nitrogen, nitrous oxide, and water. Unimolecular decompositions of NO or NH{sub 3} were not detectable under these conditions, up to 773 K. The reduction of nitric oxide with ammonia occurred in the temperature range of 548-633 K. The Arrhenius curve of the reaction showed a break in the 563-603 K range, which was slightly dependent on the reactant concentrations. In this temperature range the reaction became oscillatory. The activation energies were 102 kJ/mol in the low-temperature and 212 kJ/mol in the high-temperature ranges, respectively. The product distribution was different in the two temperature regions; in the low-temperature range the n{sub 2}/N{sub 2}O ratio was close to 1, while in the high-temperature regime N{sub 2} formation was dominant, and the previously formed N{sub 2}O was consumed as well.

  17. Large enhancement of the photovoltaic effect in ferroelectric complex oxides through bandgap reduction

    PubMed Central

    An, Hyunji; Han, Jun Young; Kim, Bongjae; Song, Jaesun; Jeong, Sang Yun; Franchini, Cesare; Bark, Chung Wung; Lee, Sanghan

    2016-01-01

    Tuning the bandgap in ferroelectric complex oxides is a possible route for improving the photovoltaic activity of materials. Here, we report the realization of this effect in epitaxial thin films of the ferroelectric complex oxide Bi3.25La0.75Ti3O12 (BLT) suitably doped by Fe and Co. Our study shows that Co (BLCT) doping and combined Fe, Co (BLFCT) doping lead to a reduction of the bandgap by more than 1 eV compared to undoped BLT, accompanied by a surprisingly more efficient visible light absorption. Both BLCT and BLFCT films can absorb visible light with a wavelength of up to 500 nm while still exhibiting ferroelectricity, whereas undoped BLT only absorbs UV light with a wavelength of less than 350 nm. Correlated with its bandgap reduction, the BLFCT film shows a photocurrent density enhanced by 25 times compared to that of BLT films. Density functional theory calculations indicate that the bandgap contraction is caused by the formation of new energy states below the conduction bands due to intermixed transition metal dopants (Fe, Co) in BLT. This mechanism of tuning the bandgap by simple doping can be applied to other wide-bandgap complex oxides, thereby enabling their use in solar energy conversion or optoelectronic applications. PMID:27313099

  18. Large enhancement of the photovoltaic effect in ferroelectric complex oxides through bandgap reduction.

    PubMed

    An, Hyunji; Han, Jun Young; Kim, Bongjae; Song, Jaesun; Jeong, Sang Yun; Franchini, Cesare; Bark, Chung Wung; Lee, Sanghan

    2016-01-01

    Tuning the bandgap in ferroelectric complex oxides is a possible route for improving the photovoltaic activity of materials. Here, we report the realization of this effect in epitaxial thin films of the ferroelectric complex oxide Bi3.25La0.75Ti3O12 (BLT) suitably doped by Fe and Co. Our study shows that Co (BLCT) doping and combined Fe, Co (BLFCT) doping lead to a reduction of the bandgap by more than 1 eV compared to undoped BLT, accompanied by a surprisingly more efficient visible light absorption. Both BLCT and BLFCT films can absorb visible light with a wavelength of up to 500 nm while still exhibiting ferroelectricity, whereas undoped BLT only absorbs UV light with a wavelength of less than 350 nm. Correlated with its bandgap reduction, the BLFCT film shows a photocurrent density enhanced by 25 times compared to that of BLT films. Density functional theory calculations indicate that the bandgap contraction is caused by the formation of new energy states below the conduction bands due to intermixed transition metal dopants (Fe, Co) in BLT. This mechanism of tuning the bandgap by simple doping can be applied to other wide-bandgap complex oxides, thereby enabling their use in solar energy conversion or optoelectronic applications. PMID:27313099

  19. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

  20. Oxide Shell Reduction and Magnetic Property Changes in Core-Shell Fe Nanoclusters under Ion Irradiation

    SciTech Connect

    Sundararajan, Jennifer A.; Kaur, Maninder; Jiang, Weilin; McCloy, John S.; Qiang, You

    2014-02-12

    Ion irradiation effects are studied on the Fe-based core-shell nanocluster (NC) films with core as Fe and shell as Fe3O4/FeO. These NC films were were deposited on Si substrates to thickness of ~0.5 micrometers using a NC deposition system. The films were irradiated at room temperature with 5.5 MeV Si2+ ions to ion fluences of 1015 and 1016 ions/cm2. It is found that the irradiation induces grain growth, Fe valence reduction in the shell, and crystallization of Fe3N. The nature and mechanism of oxide shell reduction and composition dependence after irradiation were studied by synthesizing additional NC films of Fe3O4 and FeO+Fe3N and irradiating them under the same conditions. The presence of nanocrystalline Fe is found to be a major factor for the oxide shell reduction. The surface morphologies of these films show dramatic changes in the microstructures due to cluster growth and agglomeration as a result of ion irradiation.

  1. Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes.

    PubMed

    Zayas Pérez, Teresa; Geissler, Gunther; Hernandez, Fernando

    2007-01-01

    The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes (AOP) had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H2O2, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand (COD) and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater. PMID:17918591

  2. Oxide shell reduction and magnetic property changes in core-shell Fe nanoclusters under ion irradiation

    SciTech Connect

    Sundararajan, Jennifer A.; Kaur, Maninder; Qiang, You; Jiang, Weilin; McCloy, John S.

    2014-05-07

    Ion irradiation effects are studied on the Fe-based core-shell nanocluster (NC) films with core as Fe and shell as Fe{sub 3}O{sub 4}/Fe{sub 3}N. These NC films were deposited on Si substrates to thickness of ∼0.5 μm using a NC deposition system. The films were irradiated at room temperature with 5.5 MeV Si{sup 2+} ions to ion fluences of 10{sup 15} and 10{sup 16} ions/cm{sup 2}. It is found that the irradiation induces grain growth, Fe valence reduction in the shell, and crystallization or growth of Fe{sub 3}N. The film retained its Fe-core and its ferromagnetic properties after irradiation. The nature and mechanism of oxide shell reduction and composition dependence after irradiation were studied by synthesizing additional NC films of Fe{sub 3}O{sub 4} and FeO + Fe{sub 3}N and irradiating them under the same conditions. The presence of nanocrystalline Fe is found to be a major factor for the oxide shell reduction. The surface morphologies of these films show dramatic changes in the microstructures due to cluster growth and agglomeration as a result of ion irradiation.

  3. Reduction of chemical oxygen demand of industrial wastes using subcritical water oxidation

    SciTech Connect

    Lin, J.C.; Chang, C.J. )

    1992-10-01

    If wastes have strong toxicity, high organic content, and a deep hue, they are difficult to handle in the waste disposal. It is very practical that waste of this kind is treated by Subcritical Water Oxidation (SWO). In our work, caprolactum (CPL) waste, purged from a petrochemical plant, and dyeing waste, purged from a textile plant, were individually treated by a semi-batch SWO process. Within a one-hour treatment, Chemical Oxygen Demand (COD) reduction reached 89% for CPL waste (6.90 MPa, 260[degree]C) and 95% for dyeing waste (6.90 MPa, 240[degree]C). There is also a great improvement in hue, especially for the dyeing waste. When CPL wastewater was treated by the SWO process using a chromium metal powder as a catalyst, COD reduction improved further under the same operating conditions. A kinetic model was used to illustrate the oxidation mechanism and the effectiveness of the catalyst. The oxygen concentration in the effluent showed that oxygen consumption corresponded to COD reduction. With the monitoring of concentrations of total soluble chromium in the effluent, a suitable reaction period could be found in order to meet the standard of the Environmental Protection Agency (EPA). 12 refs., 11 figs., 2 tabs.

  4. Reduction and dephosphorization of molten iron oxide with hydrogen-argon plasma

    SciTech Connect

    Nakamura, Y.; Ishikawa, H.; Ito, M.

    1981-06-01

    A laboratory-scale test was made in which iron oxide contained in a water-cooled crucible was melted and reduced by using a 10-50% H/sub 2/-Ar transferred arc plasma. The degree of reduction was found to be proportional to the amount of hydrogen fed. The efficiency of hydrogen utilization for the reduction was 50-70%, which is much higher than equilibrium values below 3000 K. This high efficiency was attributable partially to the reactivity of the hydrogen atom in a plasma and partially to the continuous contact of the hydrogen plasma with the molten iron oxide layer floating over the liquid iron formed. During the plasma reduction, evaporative loss of phosphorus was observed. The degree of phosphorus removal depended on the weight ratio, CaO/(SiO/sub 2/+Al/sub 2/O/sub 3/). H/sub 2/-Ar plasma was shown to be far superior for the phosphorus removal, compared with Ar and Ar-N/sub 2/ plasma.

  5. Reduction phases of thin iron-oxide nanowires upon thermal treatment and Li exposure

    SciTech Connect

    Angelucci, Marco Frau, Eleonora; Grazia Betti, Maria; Hassoun, Jusef; Hong, Inchul; Panero, Stefania; Scrosati, Bruno; Mariani, Carlo

    2014-04-28

    Iron oxide nanostructures, a promising alternative to carbon-based anode in lithium-ion batteries, can be produced using a hard template route. This procedure guarantees the formation of Fe{sub 2}O{sub 3} nanowires with comparable diameter and size (average diameter 8 nm) with a dominant cubic γ-phase at the surface. Lithium exposure of the iron oxide nanowires in ultra-high-vacuum (UHV) conditions induces reduction of the Fe ion, leading to a Fe{sub 3}O{sub 4} and then to a Fe{sup 2+} phase, as determined by means of core-level photoemission spectroscopy. Mild annealing of Fe{sub 2}O{sub 3} in UHV determines an oxygen content reduction for the nanowires at lower temperature with respect to the bulk phase. The morphology and the evolution of the electronic properties upon reduction have been compared to those of micro-sized bulk-like grains, to unravel the role of the reduced size and surface-volume ratio.

  6. Modeling Exposures to the Oxidative Potential of PM10

    PubMed Central

    2012-01-01

    Differences in the toxicity of ambient particulate matter (PM) due to varying particle composition across locations may contribute to variability in results from air pollution epidemiologic studies. Though most studies have used PM mass concentration as the exposure metric, an alternative which accounts for particle toxicity due to varying particle composition may better elucidate whether PM from specific sources is responsible for observed health effects. The oxidative potential (OP) of PM < 10 μm (PM10) was measured as the rate of depletion of the antioxidant reduced glutathione (GSH) in a model of human respiratory tract lining fluid. Using a database of GSH OP measures collected in greater London, U.K. from 2002 to 2006, we developed and validated a predictive spatiotemporal model of the weekly GSH OP of PM10 that included geographic predictors. Predicted levels of OP were then used in combination with those of weekly PM10 mass to estimate exposure to PM10 weighted by its OP. Using cross-validation (CV), brake and tire wear emissions of PM10 from traffic within 50 m and tailpipe emissions of nitrogen oxides from heavy-goods vehicles within 100 m were important predictors of GSH OP levels. Predictive accuracy of the models was high for PM10 (CV R2=0.83) but only moderate for GSH OP (CV R2 = 0.44) when comparing weekly levels; however, the GSH OP model predicted spatial trends well (spatial CV R2 = 0.73). Results suggest that PM10 emitted from traffic sources, specifically brake and tire wear, has a higher OP than that from other sources, and that this effect is very local, occurring within 50–100 m of roadways. PMID:22731499

  7. Oxidative potential of particulate matter at a German motorway.

    PubMed

    Hellack, Bryan; Quass, Ulrich; Nickel, Carmen; Wick, Gabriele; Schins, Roel P F; Kuhlbusch, Thomas A J

    2015-04-01

    Ambient particulate matter (PM10) was sampled alongside a motorway in North-Rhine Westphalia, Germany, during a one-year period. In sum, 120 PM10 samples on quartz fibre filters, 60 samples at each side of the motorway, were taken during clear cross-wind direction situations, i.e. upwind (local background situation) and downwind (traffic influenced). To quantify the traffic-related oxidative potential (OP), or more precisely the hydroxyl radical (OH˙) generation potency, these samples were analysed to study their hydrogen peroxide dependent oxidant generation by Electron Paramagnetic Resonance (EPR) spectroscopy using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide. In addition the PM10 mass, the chemical composition and the NOx concentrations were determined. For PM10 mass and traffic tracers like Sb, Ba, elemental and organic carbon as well as for NOx, an additional contribution to the background concentration caused by the traffic was observed (factor: 1.3-6.0). The downwind measurements showed in 72% of cases higher OH˙ generation potencies with an average factor of 1.4. Significant correlations to OH˙ were detected for Fe (r > 0.58) and Cu (r > 0.57) for the upwind and overall (upwind + downwind, r > 0.44) dataset. At the downwind side these correlations were absent and are assumed to be covered by the interferences with additional soot particles leading to a quenching of OH˙. Accordingly, no significant overall correlation of the OH˙ generation potency with the traffic intensity was detected. The suggested quenching effect was confirmed via standard diesel soot (SRM 2975) measurements using the EPR approach. In summary, the traffic related PM causes an intrinsic OH˙ generation via Fenton-like reaction but obviously also leads to interferences and scavenging by traffic related carbonaceous compounds. In consequence, for future studies that would link the intrinsic OP and adverse health effects we suggest to analyse the relationship to EC/OC and to use in

  8. ON-LINE DEOXYGENATION IN REDUCTIVE (AND OXIDATIVE) AMPEROMETRIC DETECTION: ENVIRONMENTAL APPLICATIONS IN THE LIQUID CHROMATOGRAPHY OF ORGANIC PEROXIDES

    EPA Science Inventory

    Cyclic voltammetry was used qualitatively to characterize and determine the feasibility of the oxidation and reduction of selected organic peroxides and hydroperoxides at a glassy carbon electrode. Organic peroxides were determined using reversed-phase high-performance liquid chr...

  9. Dissimilatory reduction of nitrate and nitrite in the bovine rumen: nitrous oxide production and effect of acetylene.

    PubMed Central

    Kaspar, H F; Tiedje, J M

    1981-01-01

    15N tracer methods and gas chromatography coupled to an electron capture detector were used to investigate dissimilatory reduction of nitrate and nitrite by the rumen microbiota of a fistulated cow. Ammonium was the only 15N-labeled end product of quantitative significance. Only traces of nitrous oxide were detected as a product of nitrate reduction; but in experiments with nitrite, up to 0.3% of the added nitrogen accumulated as nitrous oxide, but it was not further reduced. Furthermore, when 13NO3- was incubated with rumen microbiota virtually no [13N]N2 was produced. Acetylene partially inhibited the reduction of nitrite to ammonium as well as the formation of nitrous oxide. It is suggested that in the rumen ecosystem nitrous oxide is a byproduct of dissimilatory nitrite reduction to ammonium rather than a product of denitrification and that the latter process is absent from the rumen habitat. PMID:7224631

  10. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    DOE PAGESBeta

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

  11. Simulation of reduction of iron-oxide-carbon composite pellets in a rotary hearth furnace

    NASA Astrophysics Data System (ADS)

    Halder, Sabuj

    The primary motivation of this work is to evaluate a new alternative ironmaking process which involves the combination of a Rotary Hearth Furnace (RHF) with an iron bath smelter. This work is concerned primarily, with the productivity of the RHF. It is known that the reduction in the RHF is controlled by chemical kinetics of the carbon oxidation and wustite reduction reactions as well as by heat transfer to the pellet surface and within the pellet. It is heat transfer to the pellet which limits the number of layers of pellets in the pellet bed in the RHF and thus, the overall productivity. Different types of carbon like graphite, coal-char and wood charcoal were examined. Part of the research was to investigate the chemical kinetics by de-coupling it from the influence of heat and mass transfer. This was accomplished by carrying out reduction experiments using small iron-oxide-carbon powder composite mixtures. The reaction rate constants were determined by fitting the experimental mass loss with a mixed reaction model. This model accounts for the carbon oxidation by CO2 and wustite reduction by CO, which are the primary rate controlling surface-chemical reactions in the composite system. The reaction rate constants have been obtained using wustite-coal-char powder mixtures and wustite-wood-charcoal mixtures. The wustite for these mixtures was obtained from two iron-oxide sources: artificial porous analytical hematite (PAH) and hematite ore tailings. In the next phase of this study, larger scale experiments were conducted in a RHF simulator using spherical composite pellets. Measurement of the reaction rates was accomplished using off-gas analysis. Different combinations of raw materials for the pellets were investigated. These included artificial ferric oxide as well as naturally existing hematite and taconite ores. Graphite, coal-char and wood-charcoal were the reductants. Experiments were conducted using a single layer, a double layer and a triple layer of

  12. Hexavalent chromium reduction by tartaric acid and isopropyl alcohol in Mid-Atlantic soils and the role of Mn(III,IV)(hydr)oxides.

    PubMed

    Brose, Dominic A; James, Bruce R

    2013-11-19

    Chromium is a naturally occurring transition metal and a soil contaminant in the Cr(VI) oxidation state, but reduction<