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Sample records for oxidation reduction potentials

  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 methane and iron reduction in marine sediments. Geobiology 12, 172-181. Zillén L., Conley D. J., Andrén T., Andrén E. and Björck S. (2008) Past occurrences of hypoxia in the Baltic Sea and the role of climate variability, environmental change and human impact. Earth-Science Rev. 91, 77-92.

  4. Assessment of Eccentric Exercise-Induced Oxidative Stress Using Oxidation-Reduction Potential Markers

    PubMed Central

    Stagos, Dimitrios; Goutzourelas, Nikolaos; Ntontou, Amalia-Maria; Kafantaris, Ioannis; Deli, Chariklia K.; Poulios, Athanasios; Jamurtas, Athanasios Z.; Bar-Or, David; Kouretas, Dimitrios

    2015-01-01

    The aim of the present study was to investigate the use of static (sORP) and capacity ORP (cORP) oxidation-reduction potential markers as measured by the RedoxSYS Diagnostic System in plasma, for assessing eccentric exercise-induced oxidative stress. Nineteen volunteers performed eccentric exercise with the knee extensors. Blood was collected before, immediately after exercise, and 24, 48, and 72?h after exercise. Moreover, common redox biomarkers were measured, which were protein carbonyls, thiobarbituric acid-reactive substances, total antioxidant capacity in plasma, and catalase activity and glutathione levels in erythrocytes. When the participants were examined as one group, there were not significant differences in any marker after exercise. However, in 11 participants there was a high increase in cORP after exercise, while in 8 participants there was a high decrease. Thus, the participants were divided in low cORP group exhibiting significant decrease in cORP after exercise and in high cORP group exhibiting significant increase. Moreover, only in the low cORP group there was a significant increase in lipid peroxidation after exercise suggesting induction of oxidative stress. The results suggested that high decreases in cORP values after exercise may indicate induction of oxidative stress by eccentric exercise, while high increases in cORP values after exercise may indicate no existence of oxidative stress. PMID:25874019

  5. 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...

  6. 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 for rapid (re)formation of dissolved Cr(vi) above regulatory levels. PMID:26452013

  7. 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.

  8. 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.

  9. Development of polymer lab-on-a-chip (LOC) for oxidation-reduction potential (ORP) measurement.

    PubMed

    Jang, A; Lee, K K; Bishop, P L; Kim, I S; Ahn, C H

    2011-01-01

    Reverse osmosis (RO) desalination has been recognized as a promising method to solve the water shortage problem. Nevertheless, since it is energy intensive and has many problems associated with biofouling/fouling of RO membranes in RO plants, its commercial acceptance is still slow. Especially, as high levels of oxidizing agents negatively affect RO membrane efficiency and life span. So, there is a need to develop sensitive, selective, portable and rapid methods to determine oxidation-reduction potential (ORP) in feed solution. For developing a polymer ORP lab-on-a-chip (LOC), a microchannel patterned on a polymer substrate was successfully filled with 800 nm diameter silica beads using self-assembly bead packing technology. The measured ORPs using the three kinds of redox potential solutions were typically slightly lower than those of the nominal redox potential. But, all of the measurements should be deemed acceptable. The ORP LOC has also a much shorter response time than the conventional potentiometric sensor. PMID:21977654

  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. Reduction Potentials of Rieske Clusters: Importance of the Coupling between Oxidation State and Histidine Protonation State

    E-print Network

    Crofts, Antony R.

    (6, 7). At pH 7, Rieske cluster potentials span over 600 mV. The highest reported value, +490 m high-potential Rieske proteins have pH-dependent reduction potentials between +350 and +150 mV at pH 7, and low-potential Rieske proteins have pH-independent potentials of around -150 mV at pH 7. The pH

  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), H? (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. 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.

  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. 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.

  16. Oxidation-reduction potentials of molybdenum, flavin and iron-sulphur centres in milk xanthine oxidase.

    PubMed

    Cammack, R; Barber, M J; Bray, R C

    1976-08-01

    1. The mid-point reduction potentials of the various groups in xanthine oxidase from bovine milk were determined by potentiometric titration with dithionite in the presence of dye mediators, removing samples for quantification of the reduced species by e.p.r. (electron-paramagnetic-resonance) spectroscopy. The values obtained for the functional enzyme in pyrophosphate buffer, pH8.2, are: Fe/S centre I, -343 +/- 15mV; Fe/S II, -303 +/- 15mV; FAD/FADH-; -351 +/- 20mV; FADH/FADH2, -236 +/-mV; Mo(VI)/Mo(V) (Rapid), -355 +/- 20mV; Mo(V) (Rapid)/Mo(IV), -355 +/- 20mV. 2. Behaviour of the functional enzyme is essentially ideal in Tris but less so in pyrophosphate. In Tris, the potential for Mo(VI)/Mo(V) (Rapid) is lowered relative to that in pyrophosphate, but the potential for Fe/S II is raised. The influence of buffer on the potentials was investigated by partial-reduction experiments with six other buffers. 3. Conversion of the enzyme with cyanide into the non-functional form, which gives the Slow molybdenum signal, or alkylation of FAD, has little effect on the mid-point potentials of the other centres. The potentials associated with the Slow signal are: Mo(VI)/Mo(V) (Slow), -440 +/- 25mV; Mo(V) (Slow)/Mo(IV), -480 +/- 25 mV. This signal exhibits very sluggish equilibration with the mediator system. 4. The deviations from ideal behaviour are discussed in terms of possible binding of buffer ions or anti-co-operative interactions amongst the redox centres. PMID:183752

  17. Using oxidation-reduction potential (ORP) and pH value for process control of shortcut nitrification-denitrification.

    PubMed

    Gao, Da-Wen; Peng, Yong-Zhen; Liang, Hong; Wang, Peng

    2003-01-01

    A new low cost technology for simultaneous carbon-nitrogen removal from soybean wastewater has been developed in this study. The technology is performed through shortcut nitrification-denitrification. The process operated under realtime control of aeration and mixing time. The shortcut nitrification-denitrification in sequencing batch reactor (SBR) was achieved efficiently and steadily by controlling temperature (28 +/- 0.5 degrees C) and using real-time control strategies. This enabled the prevention of nitrite oxidation, leading to lower operational costs. The feasibility of oxidation-reduction potential (ORP) and pH value as control parameter for shortcut nitrification-denitrification process was also investigated. Results showed that the average removal efficiency of ammonium was more than 95%, and nitrosation rate (NO2(-)-N/NOx(-)-N) was reached to 96%. At the same time, the variation of oxidation--reduction potential (ORP) and pH value was well related to organic matter degradation and ammonium oxidation in SBR. So that judgment on the ending of nitrification and denitrification can be based on the inflection point on the varied curve of ORP and pH throughout each SBR processing cycle, and thus reducing aeration and mixing time for saving energy source. The method saves organic energy up to 40% of chemical oxygen demand (COD) in denitrification process, which should reduce the need for an extra external source of organic carbon. Shorter hydraulic retention time should allow the volume of the reactors to diminish, and thus diminish investment costs. Lower oxygen demand of about 25% gives lower exploitation costs. PMID:14672326

  18. Oxidation, Reduction, and Deoxygenation

    NASA Astrophysics Data System (ADS)

    Madsen, Robert

    In this chapter, methods for oxidation, reduction, and deoxygenation of carbohydrates are presented. In most cases, the reactions have been used on aldoses and their derivatives including glycosides, uronic acids, glycals, and other unsaturated monosaccharides. A number of reactions have also been applied to aldonolactones. The methods include both chemical and enzymatic procedures and some of these can be applied for regioselective transformation of unprotected or partially protected carbohydrates.

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

    E-print Network

    Konhauser, Kurt

    Reduction by Denitrifying Bacteria Nicole Klueglein,a Fabian Zeitvogel,b York-Dieter Stierhof,c Matthias and microoxic conditions. While most of the mix- otrophic nitrate-reducing Fe(II)-oxidizing bacteria become assemblage of Fe(II)-oxidizing bacteria in nature and compli- cates our ability to delineate microbial Fe

  20. Electrolytic oxide reduction system

    DOEpatents

    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).

  1. Changes in oxidation reduction potentials and volatile fatty acid production by rumen bacteria when methane synthesis is inhibited.

    PubMed

    Sauer, F D; Teather, R M

    1987-09-01

    Rumen inoculum was cultured in specially designed fermenters that allowed simultaneous measurement of pH, oxidation-reduction potentials, and gas production. The cultures were maintained at pH 6.8 by addition of 1 M NaHCO3 and continuous infusion of artificial saliva. Gas flow was maintained at 20.0 ml/min with a stream of O2-free N2. Monensin at 7.0 micrograms/ml inhibited CH4 production 49% below control concentrations. The sodium salt of 2-bromoethanesulfonic acid added at an initial concentration of 5 x 10(-5) M inhibited CH4 production by 86% and increased H2 production from less than .5 mumol/min in the control to 24.5 mumol/min in the inhibited fermenter. The redox potentials in the control fermenter remained above -.20 V and did not change with the addition of monensin. Bromoethanesulfonic acid rapidly decreased the redox potential in the fermenter to -.33 V. Volatile fatty acid production was not significantly altered by the addition of 2-bromoethanesulfonic acid. The addition of monensin gave the expected decrease in acetate:propionate ratios, decreased acetate and butyrate production, and increased valerate (but not propionate) production. PMID:2822785

  2. Reduction of vanadium-oxide monolayer structures

    NASA Astrophysics Data System (ADS)

    Schoiswohl, J.; Surnev, S.; Sock, M.; Eck, S.; Ramsey, M. G.; Netzer, F. P.; Kresse, G.

    2005-04-01

    The reduction of vanadium oxide monolayer structures on Rh(111) has been investigated by variable-temperature scanning tunneling microscopy, low energy electron diffraction, photoelectron spectroscopy of the core levels, and the valence band, and by probing the phonon spectra of the oxide structures in high-resolution electron energy loss spectroscopy. A sequence of oxide phases has been observed following the reduction from the highly oxidized (7×7)R19.1° V-oxide monolayer: (5×5) , (5×33)rect , (9×9) , and “wagon-wheel” oxide structures are formed with decreasing chemical potential of oxygen ?O . The structures have been simulated by ab initio density functional theory, and structure models are presented. The various V-oxide structures are interrelated by common V?O coordination units, and the reduction progresses mainly via the removal of V?O vanadyl groups. All oxide structures are stable at the appropriate ?O only in the two-dimensional V-oxide/Rh(111) phase diagram and are thus stabilized by the metal-oxide interface. The results demonstrate that oxides in ultrathin layer form display modified physical and chemical properties as compared to the bulk oxides.

  3. Direct electrochemical reduction of metal-oxides

    DOEpatents

    Redey, Laszlo I. (Downers Grove, IL); Gourishankar, Karthick (Downers Grove, IL)

    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.

  4. 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.

  5. 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.

  6. 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 ...

  7. 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.

  8. 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 (...

  9. 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…

  10. Oxidation reduction potential as a parameter to regulate micro-oxygen injection into anaerobic digester for reducing hydrogen sulphide concentration in biogas.

    PubMed

    Nghiem, Long D; Manassa, Patrick; Dawson, Marcia; Fitzgerald, Shona K

    2014-12-01

    This study aims to evaluate the use of oxidation reduction potential (ORP) to regulate the injection of a small amount of oxygen into an anaerobic digester for reducing H2S concentration in biogas. The results confirm that micro-oxygen injection can be effective for controlling H2S formation during anaerobic digestion without disturbing the performance of the digester. Biogas production, composition, and the removal of volatile solids (VS) and chemical oxygen demand (COD) were monitored to assessment the digester's performance. Six days after the start of the micro-oxygen injection, the ORP values increased to between -320 and -270 mV, from the natural baseline value of -485 mV. Over the same period the H2S concentration in the biogas decreased from over 6000 ppm to just 30 ppm. No discernible changes in the VS and COD removal rates, pH and alkalinity of the digestate or in the biogas production or composition were observed. PMID:25306445

  11. 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.

  12. Reduction of metal oxides through mechanochemical processing

    DOEpatents

    Froes, Francis H. (Moscow, ID); Eranezhuth, Baburaj G. (Moscow, ID); Senkov, Oleg N. (Moscow, ID)

    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.

  13. 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.

  14. Production-scale Direct Oxide Reduction demonstration

    SciTech Connect

    Humiston, T.J.; Santi, D.J.; Long, J.L.; Thomas, R.L.; Delaney, I.C.

    1989-01-23

    A detailed, statistically valid, examination of the direct oxide reduction parameters affecting process yield and purity was planned and executed. Guidelines for attaining yields approaching 100% are presented. Feed oxide, percent excess calcium, and stirrer design affected yield and product purity. Experiments were performed in production-scale equipment utilizing 800 grams of plutonium dioxide per charge. 1 ref., 9 figs., 3 tabs.

  15. 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. Successful extraction of metal from metal oxide dissolved in Urea/ChCl (2:1) was accomplished. The current efficiencies were relatively high in both the metal deposition processes with current efficiency greater than 86% for lead and 95% for zinc. This technology will advance the metal oxide reduction process by increasing the process efficiency and also eliminate the production of CO2 which makes this an environmentally benign technology for metal extraction.

  16. 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.

  17. 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.

  18. 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)

  19. In situ reduction and oxidation of nickel from solid oxide fuel cells in a Titan ETEM

    E-print Network

    Dunin-Borkowski, Rafal E.

    In situ reduction and oxidation of nickel from solid oxide fuel cells in a Titan ETEM A. Faes1. The in situ reduction and re-oxidation of the FIB prepared TEM lamellae is performed in a FEI Titan equipped

  20. 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...

  1. 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.

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

    DOEpatents

    Coops, Melvin S. (Livermore, CA)

    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.

  3. Plutonium Oxidation and Subsequent Reduction by Mn (IV) Minerals

    SciTech Connect

    KAPLAN, DANIEL

    2005-09-13

    Plutonium sorbed to rock tuff was preferentially associated with manganese oxides. On tuff and synthetic pyrolusite (Mn{sup IV}O{sub 2}), Pu(IV) or Pu(V) was initially oxidized, but over time Pu(IV) became the predominant oxidation state of sorbed Pu. Reduction of Pu(V/VI), even on non-oxidizing surfaces, is proposed to result from a lower Gibbs free energy of the hydrolyzed Pu(IV) surface species versus that of the Pu(V) or Pu(VI) surface species. This work suggests that despite initial oxidation of sorbed Pu by oxidizing surfaces to more soluble forms, the less mobile form of Pu, Pu(IV), will dominate Pu solid phase speciation during long term geologic storage. The safe design of a radioactive waste or spent nuclear fuel geologic repository requires a risk assessment of radionuclides that may potentially be released into the surrounding environment. Geochemical knowledge of the radionuclide and the surrounding environment is required for predicting subsurface fate and transport. Although difficult even in simple systems, this task grows increasingly complicated for constituents, like Pu, that exhibit complex environmental chemistries. The environmental behavior of Pu can be influenced by complexation, precipitation, adsorption, colloid formation, and oxidation/reduction (redox) reactions (1-3). To predict the environmental mobility of Pu, the most important of these factors is Pu oxidation state. This is because Pu(IV) is generally 2 to 3 orders of magnitude less mobile than Pu(V) in most environments (4). Further complicating matters, Pu commonly exists simultaneously in several oxidation states (5, 6). Choppin (7) reported Pu may exist as Pu(IV), Pu(V), or Pu(VI) oxic natural groundwaters. It is generally accepted that plutonium associated with suspended particulate matter is predominantly Pu(IV) (8-10), whereas Pu in the aqueous phase is predominantly Pu(V) (2, 11-13). The influence of the character of Mn-containing minerals expected to be found in subsurface repository environments on Pu oxidation state distributions has been the subject of much recent research. Kenney-Kennicutt and Morse (14), Duff et al. (15), and Morgenstern and Choppin (16) observed oxidation of Pu facilitated by Mn(IV)-bearing minerals. Conversely, Shaughnessy et al. (17) used X-ray Absorption near-edge spectroscopy (XANES) to show reduction of Pu(VI) by hausmannite (Mn{sup II}Mn{sub 2}{sup III}O{sub 4}) and manganite ({gamma}-Mn{sup III}OOH) and Kersting et al., (18) observed reduction of Pu(VI) by pyrolusite (Mn{sup IV}O{sub 2}). In this paper, we attempt to reconcile the apparently conflicting datasets by showing that Mn-bearing minerals can indeed oxidize Pu, however, if the oxidized species remains on the solid phase, the oxidation step competes with the formation of Pu(IV) that becomes the predominant solid phase Pu species with time. The experimental approach we took was to conduct longer term (approximately two years later) oxidation state analyses on the Pu sorbed to Yucca Mountain tuff (initial analysis reported by Duff et al., (15)) and measure the time-dependant changes in the oxidation state distribution of Pu in the presence of the Mn mineral pyrolusite.

  4. 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...

  5. 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).

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

    SciTech Connect

    Coops, M.S.

    1992-06-02

    This patent describes a method for production of plutonium metal from plutonium oxide by metallic lithium reduction, with regeneration of lithium reactant. It comprises: reacting the plutonium oxide with metallic lithium; oxides and unreacted lithium; subliming the product lithium oxide and unreacted lithium from unreacted plutonium oxide with high heat and low pressure; recapturing the product lithium oxides; reacting the recaptured product lithium oxides with anhydrous hydrochloric acid to produce lithium chloride salt; and decomposing product lithium chloride salt by electrolysis to regenerate lithium metal.

  7. 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.

  8. Highly active oxide photocathode for photoelectrochemical water reduction

    NASA Astrophysics Data System (ADS)

    Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin; Grätzel, Michael; Thimsen, Elijah

    2011-06-01

    A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H2 production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6?mA?cm-2 at a potential of 0?V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1?h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%.

  9. Highly active oxide photocathode for photoelectrochemical water reduction.

    PubMed

    Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin; Grätzel, Michael; Thimsen, Elijah

    2011-06-01

    A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H(2) production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6 mA cm(-2) at a potential of 0 V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1 h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%. PMID:21552270

  10. 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.

  11. 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…

  12. Three-electrode metal oxide reduction cell

    DOEpatents

    Dees, Dennis W. (Downers Groves, IL); Ackerman, John P. (Downers Grove, IL)

    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.

  13. Reduction–Oxidation Photocycle Dynamics of Flavins in Starch Films

    PubMed Central

    Penzkofer, Alfons

    2012-01-01

    The blue-light photo-reduction (conversion of oxidized flavin quinone via flavin semiquinone to fully reduced flavin hydroquinone) and dark re-oxidation of the flavins riboflavin and lumiflavin in starch (?-amylose) films was studied by absorption and luminescence spectroscopy. Blue-light photo-excitation caused an absorption, fluorescence, and phosphorescence decrease which recovered in the dark. The photo-reduction dark-oxidation cycle could be repeated. The efficiency of photo-reduction decreased with exposed excitation energy, and the speed of re-oxidation in the dark slowed down with time after excitation. The absorption did not fully recover. The fluorescence efficiency after a long time of storage in the dark increased beyond the initial flavin quinone fluorescence efficiency. Flavin photo-excitation is thought to cause starch-flavin restructuring (static fluorescence quenching center formation), enabling enhanced photo-induced starch to flavin electron transfer with subsequent flavin reduction and starch oxidation. In the dark, after light switch-off, thermal reversion of flavin reduction and starch oxidation occurred. PMID:22942758

  14. The Role of Surface Defects in CO Oxidation, Methanol Oxidation, and Oxygen Reduction on Pt,,111...

    E-print Network

    Kenis, Paul J. A.

    The Role of Surface Defects in CO Oxidation, Methanol Oxidation, and Oxygen Reduction on Pt,,111 as a model for terrace favored reactions. More complicated reactions, such as methanol oxidation, can of electronic structure, but methanol dehydrogenation is promoted only by step-type defects, as a result

  15. Research Articles Potential for Microbial Oxidation

    E-print Network

    Johnson, Clark M.

    ­340. 1. Introduction Iron is the fourth most abundant element in Earth's crust and is found in twoResearch Articles Potential for Microbial Oxidation of Ferrous Iron in Basaltic Glass Mai Yia Xiong, Evgenya S. Shelobolina, and Eric E. Roden Abstract Basaltic glass (BG) is an amorphous ferrous iron [Fe

  16. 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.

  17. Reductive mobilization of oxide-bound metals

    SciTech Connect

    Stone, A.T.

    1992-01-01

    This project is concerned with the mobilization of MnO{sub 2}- and FeOOH-bound toxic metals in subsurface environments arising from an influx of natural organic matter or organic-containing wastes. Our work to date emphasizes the importance of characterizing the reductant, complexant, and adsorptive characteristics of constituent organic chemicals. Organic chemicals may interact with pollutant metals directly, or may bring about changes in speciation and solubility indirectly by acting upon MnO{sub 2} and FeOOH host phases. The primary application of this work is the understanding of metal sorption and release processes within subsurface environments undergoing changes in redox status.

  18. 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.

  19. 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.

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

    DOEpatents

    Yeh, James T. (Bethel Park, PA); Ekmann, James M. (Bethel Park, PA); Pennline, Henry W. (Bethel Park, PA); Drummond, Charles J. (Churchill, PA)

    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.

  1. Discrete reduction of type I collagen thermal stability upon oxidation.

    PubMed

    Komsa-Penkova, R; Koynova, R; Kostov, G; Tenchov, B

    2000-01-24

    The oxidation of acid-soluble calf skin collagen type I caused by metal-dependent free radical generating systems, Fe(II)/H2O2 and Cu(II)/H2O2, was found to bring down in a specific, discrete way the collagen thermal stability, as determined by microcalorimetry and scanning densitometry. Initial oxidation results in splitting of the collagen denaturational transition into two components. Along with the endotherm at 41 degrees C typical for non-oxidized collagen, a second, similarly cooperative endotherm appears at 35 degrees C and increases in enthalpy with the oxidant concentration and exposure time, while the first peak correspondingly decreases. The two transitions at 35 and 41 degrees C were registered by densitometry as stepwise increases of the collagen-specific volume. Further oxidation results in massive collagen destruction manifested as abolishment of both denaturational transitions. The two oxidative systems used produce identical effects on the collagen stability but at higher concentrations of Cu(II) in comparison to Fe(II). The discrete reduction of the protein thermal stability is accompanied by a decrease of the free amino groups, suggestive of an oxidation attack of the side chains of lysine residues. Since the denaturation temperature of collagen shifts from above to below body temperature (41 degrees C-35 degrees C) upon oxidation, it appears important to account for this effect in a context of the possible physiological implications of collagen oxidation. PMID:10647849

  2. Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential.

    PubMed

    Xu, Weiwei; Li, Qian; Shang, Jing; Liu, Jia; Feng, Xiang; Zhu, Tong

    2015-10-01

    Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites. PMID:26456606

  3. Nickel oxide reduction studied by environmental TEM and in situ XRD Q. Jeangros1

    E-print Network

    Dunin-Borkowski, Rafal E.

    Nickel oxide reduction studied by environmental TEM and in situ XRD Q. Jeangros1 , T.W. Hansen2 , J, Switzerland quentin.jeangros@epfl.ch Keywords: Environmental TEM, Nickel Oxide, Reduction Nickel oxide reduction and subsequent Ni behaviour under H2 is of practical importance in the field of solid oxide fuel

  4. Removal of the X-ray contrast media diatrizoate by electrochemical reduction and oxidation.

    PubMed

    Radjenovic, Jelena; Flexer, Victoria; Donose, Bogdan C; Sedlak, David L; Keller, Jurg

    2013-01-01

    Due to their resistance to biological wastewater treatment, iodinated X-ray contrast media (ICM) have been detected in municipal wastewater effluents at relatively high concentrations (i.e., up to 100 ?g L(-1)), with hospitals serving as their main source. To provide a new approach for reducing the concentrations of ICMs in wastewater, electrochemical reduction at three-dimensional graphite felt and graphite felt doped with palladium nanoparticles was examined as a means for deiodination of the common ICM diatrizoate. The presence of palladium nanoparticles significantly enhanced the removal of diatrizoate and enabled its complete deiodination to 3,5-diacetamidobenzoic acid. When the system was employed in the treatment of hospital wastewater, diatrizoate was reduced, but the extent of electrochemical reduction decreased as a result of competing reactions with solutes in the matrix. Following electrochemical reduction of diatrizoate to 3,5-diacetamidobenzoic acid, electrochemical oxidation with boron-doped diamond (BDD) anodes was employed. 3,5-Diacetamidobenzoic acid disappeared from solution at a rate that was similar to that of diatrizoate, but it was more readily mineralized than the parent compound. When electrochemical reduction and oxidation were coupled in a three-compartment reactor operated in a continuous mode, complete deiodination of diatrizoate was achieved at an applied cathode potential of -1.7 V vs SHE, with the released iodide ions electrodialyzed in a central compartment with 80% efficiency. The resulting BDD anode potential (i.e., +3.4-3.5 V vs SHE) enabled efficient oxidation of the products of the reductive step. The presence of other anions (e.g., chloride) was likely responsible for a decrease in I(-) separation efficiency when hospital wastewater was treated. Reductive deiodination combined with oxidative degradation provides benefits over oxidative treatment methods because it does not produce stable iodinated intermediates. Nevertheless, the process must be further optimized for the conditions encountered in hospital wastewater to improve the separation efficiency of halide ions prior to the electrooxidation step. PMID:24261992

  5. 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

  6. 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.

  7. Density functional and reduction potential calculations of Fe4S4 clusters.

    PubMed

    Torres, Rhonda A; Lovell, Timothy; Noodleman, Louis; Case, David A

    2003-02-19

    Density functional theory geometry optimizations and reduction potential calculations are reported for all five known oxidation states of [Fe(4)S(4)(SCH(3))(4)](n)()(-) (n = 0, 1, 2, 3, 4) clusters that form the active sites of iron-sulfur proteins. The geometry-optimized structures tend to be slightly expanded relative to experiment, with the best comparison found in the [Fe(4)S(4)(SCH(3))(4)](2)(-) model cluster, having bond lengths 0.03 A longer on average than experimentally observed. Environmental effects are modeled with a continuum dielectric, allowing the solvent contribution to the reduction potential to be calculated. The calculated protein plus solvent effects on the reduction potentials of seven proteins (including high potential iron proteins, ferredoxins, the iron protein of nitrogenase, and the "X", "A", and "B" centers of photosystem I) are also examined. A good correlation between predicted and measured absolute reduction potentials for each oxidation state of the cluster is found, both for relative potentials within a given oxidation state and for the absolute potentials for all known couples. These calculations suggest that the number of amide dipole and hydrogen bonding interactions with the Fe(4)S(4) clusters play a key role in modulating the accessible redox couple. For the [Fe(4)S(4)](0) (all-ferrous) system, the experimentally observed S = 4 state is calculated to lie lowest in energy, and the predicted geometry and electronic properties for this state correlate well with the EXAFS and Mössbauer data. Cluster geometries are also predicted for the [Fe(4)S(4)](4+) (all-ferric) system, and the calculated reduction potential for the [Fe(4)S(4)(SCH(3))(4)](1)(-)(/0) redox couple is in good agreement with that estimated for experimental model clusters containing alkylthiolate ligands. PMID:12580620

  8. Bacteria-Mediated Arsenic Oxidation and Reduction in the Growth Media of Arsenic Hyperaccumulator Pteris vittata

    E-print Network

    Ma, Lena

    Bacteria-Mediated Arsenic Oxidation and Reduction in the Growth Media of Arsenic Hyperaccumulator, Nanjing University, Jiangsu 210046, China ABSTRACT: Microbes play an important role in arsenic transformation and cycling in the environment. Microbial arsenic oxidation and reduction were demonstrated

  9. 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.

  10. Catalysis of Reduction and Oxidation Reactions for Application in Gas Particle Filters

    SciTech Connect

    Udron, L.; Turek, T.

    2002-09-19

    The present study is a first part of an investigation addressing the simultaneous occurrence of oxidation and reduction reactions in catalytic filters. It has the objectives (a) to assess the state of knowledge regarding suitable (types of) catalysts for reduction and oxidation, (b) to collect and analyze published information about reaction rates of both NOx reduction and VOC oxidation, and (c) to adjust a lab-scale screening method to the requirements of an activity test with various oxidation/reduction catalysts.

  11. Reduction of nitrite to nitric oxide catalyzed by xanthine oxidoreductase.

    PubMed

    Godber, B L; Doel, J J; Sapkota, G P; Blake, D R; Stevens, C R; Eisenthal, R; Harrison, R

    2000-03-17

    Xanthine oxidase (XO) was shown to catalyze the reduction of nitrite to nitric oxide (NO), under anaerobic conditions, in the presence of either NADH or xanthine as reducing substrate. NO production was directly demonstrated by ozone chemiluminescence and showed stoichiometry of approximately 2:1 versus NADH depletion. With xanthine as reducing substrate, the kinetics of NO production were complicated by enzyme inactivation, resulting from NO-induced conversion of XO to its relatively inactive desulfo-form. Steady-state kinetic parameters were determined spectrophotometrically for urate production and NADH oxidation catalyzed by XO and xanthine dehydrogenase in the presence of nitrite under anaerobic conditions. pH optima for anaerobic NO production catalyzed by XO in the presence of nitrite were 7.0 for NADH and reduction was shown by the fact that alloxanthine inhibits xanthine oxidation competitively with nitrite. Strong preference for Mo=S over Mo=O was shown by the relatively very low NADH-nitrite reductase activity shown by desulfo-enzyme. The FAD site of XO was shown not to influence nitrite reduction in the presence of xanthine, although it was clearly involved when NADH was the reducing substrate. Apparent production of NO decreased with increasing oxygen tensions, consistent with reaction of NO with XO-generated superoxide. It is proposed that XO-derived NO fulfills a bactericidal role in the digestive tract. PMID:10713088

  12. 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.

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

    DOEpatents

    Miller, William E. (Naperville, IL); Tomczuk, Zygmunt (Lockport, IL)

    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. 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.

  15. Thermoelectric Powder Using an Oxide-Reduction Process

    NASA Astrophysics Data System (ADS)

    Lee, Gilgeun; Ha, Gookhyun

    2014-06-01

    The present study focused on synthesis of Bi0.5Sb1.5Te3 thermoelectric powder using an oxide-reduction process. The phase structure and particle size of the synthesized powders were analyzed using x-ray diffractometry and scanning electron microscopy. The synthesized powder was sintered using the spark plasma sintering method. The thermoelectric properties of the sintered body were evaluated by measuring the Seebeck coefficient, electrical resistivity, and thermal conductivity. Bi0.5Sb1.5Te3 powder was synthesized using a combination of mechanical milling, calcination, and reduction processes, using a mixture of Bi2O3, Sb2O3, and TeO2 powders. The sintered body of the oxide-reduction-synthesized Bi0.5Sb1.5Te3 powder showed p-type thermoelectric characteristics. The thermoelectric properties of the sintered bodies depended on the reduction time. After being reduced for 2 h at 663 K, the sintered body of the Bi0.5Sb1.5Te3 powder showed a figure of merit of approximately 1.0 at room temperature.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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/cm3 in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

  17. 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.

  18. Reduction of nitric oxide catalyzed by hydroxylamine oxidoreductase from an anammox bacterium.

    PubMed

    Irisa, Tatsuya; Hira, Daisuke; Furukawa, Kenji; Fujii, Takao

    2014-12-01

    The hydroxylamine oxidoreductase (HAO) from the anammox bacterium, Candidatus Kuenenia stuttgartiensis has been reported to catalyze the oxidation of hydroxylamine (NH2OH) to nitric oxide (NO) by using bovine cytochrome c as an oxidant. In contrast, we investigated whether the HAO from anammox bacterium strain KSU-1 could catalyze the reduction of NO with reduced benzyl viologen (BVred) and the NO-releasing reagent, NOC 7. The reduction proceeded, resulting in the formation of NH2OH as a product. The oxidation rate of BVred was proportional to the concentration of BVred itself for a short period in each experiment, a situation that was termed quasi-steady state. The analyses of the states at various concentrations of HAO allowed us to determine the rate constant for the catalytic reaction, (2.85 ± 0.19) × 10(5) M(-1) s(-1), governing NO reduction by BVred and HAO, which was comparable to that reported for the HAO from the ammonium oxidizer, Nitrosomonas with reduced methyl viologen. These results suggest that the anammox HAO functions to adjust anammox by inter-conversion of NO and NH2OH depending on the redox potential of the physiological electron transfer protein in anammox bacteria. PMID:24996970

  19. 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 ?g Fe(III) g-1 d-1 in the annual grassland soil, 1205 ± 42 ?g Fe(III) g-1 d-1 in the drained peatland soil, and 826 ± 54 ?g 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 ?g Fe(III) g-1 in the annual grassland, 7.49 ?g Fe(III) g-1 in the drained peatland, and 20.84 ± 0.19 ?g 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 reduction rates typically decreased by day 5, associated with an increase in CH4 concentrations suggesting that potentially reducible Fe was depleted. Our results suggest that upland soils have the potential to exhibit high short-term rates of Fe reduction that may play a role in driving C oxidation and other soil biogeochemical cycles during periods of anaerobiosis.

  20. 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.

  1. 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.

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

    PubMed

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

    2015-07-17

    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. PMID:26120077

  3. 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.

  4. 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…

  5. 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.

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

    DOEpatents

    Tsang, Floris Y. (Walnut Creek, CA)

    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.

  7. 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 (?-Fe2O3) maghemite (?- Fe2O3), goethite (?-FeOOH), lepidocrocite (?-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 oxide particles in mineral dust and iodide trapped in ice or snow media (acidic aerosol, ice/snow on sea ice, icebergs, ice sheets, etc) might follow ice (photo-)chemical processes and can provide bioavailable iron and active iodine species when they melt.

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

    PubMed

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

    2015-12-01

    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?oxidation-reduction equilibrium within the growing cells. PMID:25119294

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

    DOEpatents

    Hsiao, Mark C. (Livermore, CA); Merritt, Bernard T. (Livermore, CA); Penetrante, Bernardino M. (San Ramon, CA); Vogtlin, George E. (Fremont, CA)

    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.

  10. 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.

  11. 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.

  12. Reduction of graphene oxide film with poly (vinyl alcohol)

    NASA Astrophysics Data System (ADS)

    Ahn, Sung Il; Kim, Kukjoo; Jung, Ju Ra; Kang, Keong Yeon; Lee, Seon Min; Han, Ji Ye; Choi, Kyung Cheol

    2015-04-01

    Graphene oxide (GO), products with various proportions of polyvinyl alcohol (PVA), was characterized to obtain verified patterns of reduced graphene oxide. FT-IR spectra indicated that PVA could lower the reduction temperature of GO by at around 70 °C. New peaks near D band and overlapped G band in the Raman spectra appear to indicate that some parts of PVA interact with GO. The sheet resistance of GO/PVA showed that the GO/PVA ratio was optimal between 1/0.25 and 1/2. Using GO/PVA, we printed a line on PET, and after annealing at 140 °C, it achieved a resistance of 23 k?/cm.

  13. 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 ?dmsE, but had no effect on the HFO reduction by ?dmsB, 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 ?dmsE. Bioelectrochemical analysis show that DMSO also promoted the extracellular electron transfer of WT and ?dmsE. 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

  14. 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

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

    PubMed

    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

  16. 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.

  17. 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.

  18. Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes.

    PubMed

    Liang, Yongye; Wang, Hailiang; Diao, Peng; Chang, Wesley; Hong, Guosong; Li, Yanguang; Gong, Ming; Xie, Liming; Zhou, Jigang; Wang, Jian; Regier, Tom Z; Wei, Fei; Dai, Hongjie

    2012-09-26

    Electrocatalyst for oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and energy-intensive industries. The design and synthesis of highly active ORR catalysts with strong durability at low cost is extremely desirable but remains challenging. Here, we used a simple two-step method to synthesize cobalt oxide/carbon nanotube (CNT) strongly coupled hybrid as efficient ORR catalyst by directly growing nanocrystals on oxidized multiwalled CNTs. The mildly oxidized CNTs provided functional groups on the outer walls to nucleate and anchor nanocrystals, while retaining intact inner walls for highly conducting network. Cobalt oxide was in the form of CoO due to a gas-phase annealing step in NH(3). The resulting CoO/nitrogen-doped CNT (NCNT) hybrid showed high ORR current density that outperformed Co(3)O(4)/graphene hybrid and commercial Pt/C catalyst at medium overpotential, mainly through a 4e reduction pathway. The metal oxide/carbon nanotube hybrid was found to be advantageous over the graphene counterpart in terms of active sites and charge transport. Last, the CoO/NCNT hybrid showed high ORR activity and stability under a highly corrosive condition of 10 M NaOH at 80 °C, demonstrating the potential of strongly coupled inorganic/nanocarbon hybrid as a novel catalyst system in oxygen depolarized cathode for chlor-alkali electrolysis. PMID:22957510

  19. Biodegradation potential of wastewater micropollutants by ammonia-oxidizing bacteria

    E-print Network

    Chu, Kung-Hui "Bella"

    Biodegradation potential of wastewater micropollutants by ammonia-oxidizing bacteria Hyungkeun Roh Available online xxxx Keywords: Triclosan Bisphenol A Ibuprofen Ammonia-oxidizing bacteria Nitrosomonas and mixed ammonia-oxidizing bacteria in nitrify- ing activated sludge. N. europaea could degrade triclosan

  20. Reductive potential - a savior turns stressor in protein aggregation cardiomyopathy.

    PubMed

    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 constitute a major stimulus 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, as that of OS. In addition, from our own findings we strongly believe that constitutive activation of pathways that enable sustained generation of reducing equivalents of 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

  1. ENERGY MATERIALS & THERMOELECTRICS Reduction of nickel oxide particles by hydrogen studied

    E-print Network

    Dunin-Borkowski, Rafal E.

    ENERGY MATERIALS & THERMOELECTRICS Reduction of nickel oxide particles by hydrogen studied with the ETEM observations. Introduction Nickel oxide (NiO) reduction and the subsequent Ni behaviour online: 28 November 2012 Ó Springer Science+Business Media New York 2012 In situ reduction of nickel

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

    SciTech Connect

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

    1990-11-01

    We measured potential rates of bacterial dissimilatory reduction of {sup 75}SeO{sub 4}{sup 2{minus}} to {sup 75}Se{sup 0} 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. Results indicate that a capacity for microbial selenate reduction is a common feature of a diversity of surficial sediment types in nature. Potential DSeR did not correlate with a variety of chemical factors (salinity, pH, or organic carbon) but was related to bacterial activity expressed as potential denitrification. Furthermore, the expression of potential selenate reduction activity in sediments appears to be limited by the concentration of selenate in a manner that displays Michaelis-Menten kinetics. The extent to which the presence of other group VI oxyanions or nitrate may inhibit selenate reduction appears to vary in different milieus.

  3. 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 ?* 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 ?* 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 catalytic activities. Using the established molecular principle, we further demonstrate that an alkaline earth cobalt oxide with a chemical formula of Ba0.5Sr0.5Co0.8Fe0.2O3-? (BSCF), catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than the state-of-the-art iridium oxide catalyst in basic solutions. [4pt] [1] J. Suntivich, H.A. Gasteiger, N. Yabuuchi, H. Nakanishi, J. B. Goodenough and Y. Shao-Horn, Design Principles for Oxygen Reduction Activity on Perovskite Oxide Catalysts for Fuel Cells and Metal-Air Batteries, Nature Chemistry, 3, 546--550 (2011).[0pt] [2] Jin Suntivich, Kevin J. May, Hubert A. Gasteiger, John B. Goodenough and Yang Shao-Horn, A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles, ScienceExpress, Science DOI: 10.1126/science.1212858, (2011).

  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. 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.

  6. 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.

  7. 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

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

    SciTech Connect

    Dr. Subodh K. Das; Shridas Ningileri

    2006-03-17

    This project led to an improved understanding of the mechanisms of dross formation. The microstructural evolution in industrial dross samples was determined. Results suggested that dross that forms in layers with structure and composition determined by the local magnesium concentration alone. This finding is supported by fundamental studies of molten metal surfaces. X-ray photoelectron spectroscopy data revealed that only magnesium segregates to the molten aluminum alloy surface and reacts to form a growing oxide layer. X-ray diffraction techniques that were using to investigate an oxidizing molten aluminum alloy surface confirmed for the first time that magnesium oxide is the initial crystalline phase that forms during metal oxidation. The analytical techniques developed in this project are now available to investigate other molten metal surfaces. Based on the improved understanding of dross initiation, formation and growth, technology was developed to minimize melt loss. The concept is based on covering the molten metal surface with a reusable physical barrier. Tests in a laboratory-scale reverberatory furnace confirmed the results of bench-scale tests. The main highlights of the work done include: A clear understanding of the kinetics of dross formation and the effect of different alloying elements on dross formation was obtained. It was determined that the dross evolves in similar ways regardless of the aluminum alloy being melted and the results showed that amorphous aluminum nitride forms first, followed by amorphous magnesium oxide and crystalline magnesium oxide in all alloys that contain magnesium. Evaluation of the molten aluminum alloy surface during melting and holding indicated that magnesium oxide is the first crystalline phase to form during oxidation of a clean aluminum alloy surface. Based on dross evaluation and melt tests it became clear that the major contributing factor to aluminum alloy dross was in the alloys with Mg content. Mg was 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.

  9. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C. (Los Alamos, NM)

    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).

  10. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C. (Los Alamos, NM)

    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).

  11. Redox-Inactive Metals Modulate the Reduction Potential in Heterometallic Manganese-Oxido Clusters

    PubMed Central

    Tsui, Emily Y.; Tran, Rosalie; Yano, Junko; Agapie, Theodor

    2013-01-01

    Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but their roles in catalysis are currently not well understood. A series of high oxidation state tetranuclear-dioxido clusters comprised of three manganese centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Mn3M(?4-O)(?2-O) core that remains intact upon changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV, dependent upon the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between reduction potential and acidity with a slope of ca. 100 mV per pKa unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behavior of the OEC, which is active only in the presence of one of these two metals. PMID:23511417

  12. Redox-inactive metals modulate the reduction potential in heterometallic manganese-oxido clusters

    NASA Astrophysics Data System (ADS)

    Tsui, Emily Y.; Tran, Rosalie; Yano, Junko; Agapie, Theodor

    2013-04-01

    Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but, at present, their roles in catalysis are not well understood. Here, we report a series of high-oxidation-state tetranuclear-dioxido clusters comprising three manganese centres and a redox-inactive metal (M). Crystallographic studies show an unprecedented Mn3M(µ4-O)(µ2-O) core that remains intact on changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV and are dependent on the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds demonstrate a linear dependence between reduction potential and acidity with a slope of ˜100 mV per pKa unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behaviour of the oxygen-evolving complex of photosystem II, which is active only if one of these two metals is present.

  13. Rheostat Re-Wired: Alternative Hypotheses for the Control of Thioredoxin Reduction Potentials

    PubMed Central

    Bewley, Kathryn D.; Dey, Mishtu; Bjork, Rebekah E.; Mitra, Sangha; Chobot, Sarah E.; Drennan, Catherine L.; Elliott, Sean J.

    2015-01-01

    Thioredoxins are small soluble proteins that contain a redox-active disulfide (CXXC). These disulfides are tuned to oxidizing or reducing potentials depending on the function of the thioredoxin within the cell. The mechanism by which the potential is tuned has been controversial, with two main hypotheses: first, that redox potential (Em) is specifically governed by a molecular ‘rheostat’—the XX amino acids, which influence the Cys pKa values, and thereby, Em; and second, the overall thermodynamics of protein folding stability regulates the potential. Here, we use protein film voltammetry (PFV) to measure the pH dependence of the redox potentials of a series of wild-type and mutant archaeal Trxs, PFV and glutathionine-equilibrium to corroborate the measured potentials, the fluorescence probe BADAN to measure pKa values, guanidinium-based denaturation to measure protein unfolding, and X-ray crystallography to provide a structural basis for our functional analyses. We find that when these archaeal thioredoxins are probed directly using PFV, both the high and low potential thioredoxins display consistent 2H+:2e- coupling over a physiological pH range, in conflict with the conventional ‘rheostat’ model. Instead, folding measurements reveals an excellent correlation to reduction potentials, supporting the second hypothesis and revealing the molecular mechanism of reduction potential control in the ubiquitous Trx family. PMID:25874934

  14. 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.

  15. 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.

  16. Fixed bed reduction of hematite under alternating reduction and oxidation cycles

    SciTech Connect

    Breault, Ronald W.; Monazam, Esmail R.

    2015-02-28

    The rate of the reduction reaction of a low cost natural hematite oxygen carrier for chemical looping combustion was investigated in a fixed bed reactor where hematite samples of about 1 kg were exposed to a flowing stream of methane and argon. The investigation aims to develop understanding of the factors that govern the rate of reduction with in larger reactors as compared to mostly TGA investigations in the literature. Comparison of the experimental data with a model indicated that reaction between the methane and the iron oxide shows multi-step reactions. The analysis also shows that the conversion occurs with a process that likely consumes all the oxygen close to the surface of the hematite particles and another process that is likely controlled by the diffusion of oxygen to the surface of the particles. Additional analysis shows that the thickness of the fast layer is on the order of 8 unit crystals. This is about 0.4% of the hematite; however, it comprises about 20 to 25% of the conversion for the 10 min reduction cycle.

  17. Fixed bed reduction of hematite under alternating reduction and oxidation cycles

    DOE PAGESBeta

    Breault, Ronald W.; Monazam, Esmail R.

    2015-02-28

    The rate of the reduction reaction of a low cost natural hematite oxygen carrier for chemical looping combustion was investigated in a fixed bed reactor where hematite samples of about 1 kg were exposed to a flowing stream of methane and argon. The investigation aims to develop understanding of the factors that govern the rate of reduction with in larger reactors as compared to mostly TGA investigations in the literature. Comparison of the experimental data with a model indicated that reaction between the methane and the iron oxide shows multi-step reactions. The analysis also shows that the conversion occurs withmore »a process that likely consumes all the oxygen close to the surface of the hematite particles and another process that is likely controlled by the diffusion of oxygen to the surface of the particles. Additional analysis shows that the thickness of the fast layer is on the order of 8 unit crystals. This is about 0.4% of the hematite; however, it comprises about 20 to 25% of the conversion for the 10 min reduction cycle.« less

  18. 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

    Iron (oxy)hydroxides are ubiquitous components of surfacial materials and are often the dominant redox buffering solid phases in soils and sediments. As a result, the geochemical behavior of these minerals has a profound influence on the global biogeochemical cycling of trace elements, including heavy metals and arsenic (As), in addition to nutrients such as, sulfur (S), carbon (C), nitrogen (N), and phosphorus (P). Understanding the behavior of trace elements and nutrients during biological and abiotic processes that effect iron (Fe) mineral phase transformations is paramount for predicting their distribution, mobility, and bioavailability in the environment. To evaluate the impact of dissimilatory Fe-reduction (DIR) on trace element mobility we have conducted batch incubations of Fe-rich lateritic lacustrine sediments. In contrast to mid-latitude lakes where Fe (oxy)hydroxides constitute only a small fraction of the total sediment, tropical lake sediments have been known to comprise up to 40-60 wt. % Fe-oxides. Under suboxic and nonsulphidogenic conditions it is likely that DIR plays a prominent role in early diagenesis and therefore may exert control on the fate and distribution of many trace elements in this environment (e.g. Crowe et al. 2004). In batch incubations conducted in a minimal media of similar composition to typical freshwater the lacustrine Fe-oxides were reductively dissolved at a rate very similar to pure synthetic goethite of similar surface area (measured by N2-BET). This is in contrast to the slower rates previously observed for trace element substituted Fe-oxides. These slower rates have been attributed to surface passivation by secondary Al and Cr mineral precipitation. We propose that these passivation effects may be offset in minimal media incubations by enhanced microbial metabolism due the presence of nutrients (P, Co and other metals) in the lacustrine Fe-oxides. These nutrients became available with progressive reduction as the 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.

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

    PubMed

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

    2015-05-01

    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. PMID:26026562

  20. 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.

  1. 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?.

  2. 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

  3. 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

  4. 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

  5. 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.

  6. 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

  7. 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

  8. Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

    PubMed Central

    Tsui, Emily Y.; Agapie, Theodor

    2013-01-01

    Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer. PMID:23744039

  9. 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 raises interesting questions as to what the alternative metabolic roles for the various nitrate reductases could be, analogous to the alternative metabolic roles found for nitrite reductases. PMID:24728381

  10. 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

  11. 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

  12. 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.

  13. Using FISH-SIMS to Study Marine Methane Oxidation Coupled to the Reduction of Metal Oxides, a Plausible Microbial Metabolism for Subsurface Mars

    NASA Astrophysics Data System (ADS)

    House, C. H.; Beal, E. J.; Orphan, V. J.

    2010-04-01

    In the shallow martian subsurface, microbial life could be supported by methane oxidation coupled to the reduction of sulfate or metal oxides. Here, we report results of efforts to characterize the organisms involved in manganese-dependent marine methane oxidation.

  14. Proton pump inhibitors: potential cost reductions by applying prescribing guidelines

    PubMed Central

    2012-01-01

    Background There are concerns that proton pump inhibitors (PPI) are being over prescribed in both primary and secondary care. This study aims to establish potential cost savings in a community drug scheme for a one year period according to published clinical and cost-effective guidelines for PPI prescribing. Methods Retrospective population-based cohort study in the Republic of Ireland using the Health Services Executive (HSE) Primary Care Reimbursement Services (PCRS) pharmacy claims database. The HSE-PCRS scheme is means tested and provides free health care including medications to approximately 30% of the Irish population. Prescription items are WHO ATC coded and details of every drug dispensed and claimants’ demographic data are available. Potential cost savings (net ingredient cost) were estimated according to UK NICE clinical guidelines for all HSE-PCRS claimants on PPI therapy for ?3 consecutive months starting in 2007 with a one year follow up (n=167,747). Five scenarios were evaluated; (i) change to PPI initiation (cheapest brand); and after 3 months (ii) therapeutic switching (cheaper brand/generic equivalent); (iii) dose reduction (maintenance therapy); (iv) therapeutic switching and dose reduction and (v) therapeutic substitution (H2 antagonist). Results Total net ingredient cost was €88,153,174 for claimants on PPI therapy during 2007. The estimated costing savings for each of the five scenarios in a one year period were: (i) €36,943,348 (42% reduction); (ii) €29,568,475 (34%); (iii) €21,289,322 (24%); (iv) €40,505,013 (46%); (v) €34,991,569 (40%). Conclusion There are opportunities for substantial cost savings in relation to PPI prescribing if implementation of clinical guidelines in terms of generic substitution and step-down therapy is implemented on a national basis. PMID:23163956

  15. 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 dissolved Fe{sup 2+} on the fate of ferrihydrite during reduction in structured soils.

  16. 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, ? 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 ? 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

  17. Immobilization of strontium during iron biomineralization coupled to dissimilatory hydrous ferric oxide reduction

    NASA Astrophysics Data System (ADS)

    Roden, Eric E.; Leonardo, Michael R.; Ferris, F. Grant

    2002-09-01

    The potential for incorporation of strontium (Sr) into biogenic Fe(II)-bearing minerals formed during microbial reduction of synthetic hydrous ferric oxide (HFO) was investigated in circumneutral bicarbonate-buffered medium containing SrCl 2 at concentrations of 10 ?M, 100 ?M, or 1.0 mM. CaCl 2 (10 mM) was added to some experiments to simulate a Ca-rich groundwater. In Ca-free systems, 89 to 100% of total Sr was captured in solid-phase compounds formed during reduction of 30 to 40 mmol Fe(III) L -1 over a 1-month period. A smaller fraction of total Sr (25 to 34%) was incorporated into the solid phase in cultures amended with 10 mM CaCl 2. X-ray diffraction identified siderite and ferroan ankerite as major end products of HFO reduction in Ca-free and Ca-amended cultures, respectively. Scanning electron microscopy-energy dispersive x-ray spectroscopy revealed the presence of Sr associated with carbonate phases. Selective extraction of HFO reduction end products indicated that 46 to 100% of the solid-phase Sr was associated with carbonates. The sequestration of Sr into carbonate phases in the Ca-free systems occurred systematically according to a heterogeneous (Doerner-Hoskins) partition coefficient (D D-H) of 1.81 ± 0.15. This D D-H value was 2 to 10 times higher than values determined for incorporation of Sr (10 ?M) into FeCO 3(s) precipitated abiotically at rates comparable to or greater than rates observed during HFO reduction, and fivefold higher than theoretical partition coefficients for equilibrium Fe(Sr)CO 3 solid solution formation. Surface complexation and entrapment of Sr by rapidly growing siderite crystals (and possibly other biogenic Fe(II) solids) provides an explanation for the intensive scavenging of Sr in the Ca-free systems. The results of abiotic siderite precipitation experiments in the presence and absence of excess Ca indicate that substitution of Ca for Sr at foreign element incorporation sites (mass action effect) on growing FeCO 3(s) surfaces can account for the inhibition of Sr incorporation into the siderite component of ankerite formed in the Ca-amended HFO reduction experiments. Likewise, substitution of Fe(II) for Sr may explain the absence of major Sr partitioning into the calcite component of ankerite. The findings indicate that under appropriate conditions, sequestration of metals in siderite produced during bacterial Fe(III) oxide reduction may provide a mechanism for retarding the migration of Sr and other divalent metal contaminants in anaerobic, carbonate-rich sedimentary environments.

  18. Impedance Studies of Ru Oxide Reduction in Sulfuric Acid Pranav P. Sharma and Ian Ivar Suni*,z

    E-print Network

    Suni, Ian Ivar

    Impedance Studies of Ru Oxide Reduction in Sulfuric Acid Pranav P. Sharma and Ian Ivar Suni and impedance studies of Ru oxide reduction in 1.25 M H2SO4. Voltammetry studies suggest that Ru oxide reduction may be difficult for samples exposed to laboratory air for extended times. Impedance studies show

  19. 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 accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

  20. 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

  1. High-Quality Reduced Graphene Oxide by a Dual-Function Chemical Reduction and Healing Process

    PubMed Central

    Some, Surajit; Kim, Youngmin; Yoon, Yeoheung; Yoo, HeeJoun; Lee, Saemi; Park, Younghun; Lee, Hyoyoung

    2013-01-01

    A new chemical dual-functional reducing agent, thiophene, was used to produce high-quality reduced graphene oxide (rGO) as a result of a chemical reduction of graphene oxide (GO) and the healing of rGO. Thiophene reduced GO by donation of electrons with acceptance of oxygen while it was converted into an intermediate oxidised polymerised thiophene that was eventually transformed into polyhydrocarbon by loss of sulphur atoms. Surprisingly, the polyhydrocarbon template helped to produce good-quality rGOC (chemically reduced) and high-quality rGOCT after thermal treatment. The resulting rGOCT nanosheets did not contain any nitrogen or sulphur impurities, were highly deoxygenated and showed a healing effect. Thus the electrical properties of the as-prepared rGOCT were superior to those of conventional hydrazine-produced rGO that require harsh reaction conditions. Our novel dual reduction and healing method with thiophene could potentially save energy and facilitate the commercial mass production of high-quality graphene. PMID:23722643

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

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the 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 binding of H2O on the internal and external surfaces and may be critical to catalysis in bo

  3. Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction.

    PubMed

    Weber, Karrie A; Achenbach, Laurie A; Coates, John D

    2006-10-01

    Iron (Fe) has long been a recognized physiological requirement for life, yet for many microorganisms that persist in water, soils and sediments, its role extends well beyond that of a nutritional necessity. Fe(II) can function as an electron source for iron-oxidizing microorganisms under both oxic and anoxic conditions and Fe(III) can function as a terminal electron acceptor under anoxic conditions for iron-reducing microorganisms. Given that iron is the fourth most abundant element in the Earth's crust, iron redox reactions have the potential to support substantial microbial populations in soil and sedimentary environments. As such, biological iron apportionment has been described as one of the most ancient forms of microbial metabolism on Earth, and as a conceivable extraterrestrial metabolism on other iron-mineral-rich planets such as Mars. Furthermore, the metabolic versatility of the microorganisms involved in these reactions has resulted in the development of biotechnological applications to remediate contaminated environments and harvest energy. PMID:16980937

  4. 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.

  5. 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.

  6. 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.

  7. Method For Selective Catalytic Reduction Of Nitrogen Oxides

    DOEpatents

    Mowery-Evans, Deborah L. (Broomfield, CO); Gardner, Timothy J. (Albuquerque, NM); McLaughlin, Linda I. (Albuquerque, NM)

    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.

  8. Method for selective catalytic reduction of nitrogen oxides

    DOEpatents

    Mowery-Evans, Deborah L. (Broomfield, CO); Gardner, Timothy J. (Albuquerque, NM); McLaughlin, Linda I. (Albuquerque, NM)

    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. Oxygen Reduction Kinetics Enhancement on a 2 Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    SciTech Connect

    Crumlin, Ethan; Mutoro, Eva; Ahn, Sung Jin; Jose la O', Gerardo; Leonard, Donovan N; Borisevich, Albina Y; Biegalski, Michael D; Christen, Hans M; Shao-Horn, Yang

    2010-01-01

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of {approx}85 nm thick La{sub 0.8}Sr{sub 0.2}CoO{sub 3-{delta}} (LSC{sub 113}) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced ({approx} 3-4 orders of magnitude above bulk LSC{sub 113}) by surface decorations of (La{sub 0.5}Sr{sub 0.5}){sub 2}CoO{sub 4{+-}{delta}} (LSC{sub 214}) with coverage in the range from {approx}0.1 to {approx}15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC{sub 113}/LSC{sub 214} regions, which were shown to be atomically sharp.

  10. Effect of additives on the reduction of nitrogen oxides using cyanuric acid 

    E-print Network

    Standridge, Brad Lee

    1994-01-01

    heterogeneous catalyst, yet is capable under appropriate conditions of reducing over 90% of the NO. The primary product of the NO reduction mechanism is not molecular nitrogen, but rather nitrous oxide (N20). This thesis presents an experimental investigation...

  11. Electronic structure of perovskite oxide surfaces at elevated temperatures and its correlation with oxygen reduction reactivity

    E-print Network

    Chen, Yan, Ph. D. Massachusetts Institute of Technology

    2014-01-01

    The objective is to understand the origin of the local oxygen reduction reaction (ORR) activity on the basis of the local electronic structure at the surface of transition metal oxides at elevated temperatures and in oxygen ...

  12. Kinetic modeling of nitric oxide removal from exhaust gases by Selective Non-Catalytic Reduction 

    E-print Network

    Chenanda, Cariappa Mudappa

    1993-01-01

    Selective Non-Catalytic Reduction is one of the most promising techniques for the removal of oxides of nitrogen from combustion exhaust gases. These techniques are based on the injection of certain compounds, such as cyanuric acid and ammonia...

  13. 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.

  14. 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

    There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of the most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary 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.

  15. 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.

  16. 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.

  17. IN-SITU CHEMICAL OXIDATION - DNAPL MASS REDUCTION TECHNOLOGY

    EPA Science Inventory

    In-situ chemical oxidation (ISCO) is a rapidly developing technology used at hazardous waste sites where oxidants and complimentary reagents are injected into the subsurface to transform organic contaminants into less toxic byproducts. This technology is being used at new sites ...

  18. 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.

  19. Nitrous oxide reduction by members of the family Rhodospirillaceae and the nitrous oxide reductase of Rhodopseudomonas capsulata

    SciTech Connect

    McEwan, A.G.; Greenfield, A.J.; Wetzstein, H.G.; Jackson, J.B.; Ferguson, S.J.

    1985-11-01

    After growth in the absence of nitrogenous oxides under anaerobic phototrophic conditions, several strains of Rhodopseudomonas capsulata were shown to possess a nitrous oxide reductase activity. The enzyme responsible for this activity had a periplasmic location and resembled a nitrous oxide reductase purified from Pseudomonas perfectomarinus. Electron flow to nitrous oxide reductase was coupled to generation of a membrane potential and inhibited by rotenone but not antimycin. It is suggested that electron flow to nitrous oxide reductase branches at the level of ubiquinone from the previously characterized electron transfer components of R. capsulata. R. capsulata grew under dark anaerobic conditions in the presence of malate as carbon source and nitrous oxide as electron acceptor. This confirms that nitrous oxide respiration is linked to ATP synthesis. Phototrophically and anaerobically grown cultures of nondenitrifying strains of Rhodopseudomonas sphaeroides, Rhodopseudomonas palustris, and Rhodospirillum rubrum also possessed nitrous oxide reductase activity.

  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. 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.

  2. 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.

  3. 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.

  4. 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

  5. Reversible phenol oxidation-reduction in the structurally well-defined 2-mercaptophenol-?3C protein†,‡

    PubMed Central

    Tommos, Cecilia; Valentine, Kathleen G.; Martínez-Rivera, Melissa C.; Liang, Li; Moorman, Veronica R.

    2013-01-01

    2-mercaptophenol-?3C serves as a biomimetic model for enzymes that use tyrosine residues in redox catalysis and multistep electron transfer. This model protein was tailored for electrochemical studies of phenol oxidation-reduction with specific emphasis on the redox-driven protonic reactions occurring at the phenol oxygen. This protein contains a covalently modified 2-mercaptophenol-cysteine residue. The radical site and the phenol compound were specifically chosen to bury the phenol OH group inside the protein. A solution nuclear magnetic resonance structural analysis: (i) demonstrates that the synthetic 2-mercaptophenol-?3C model protein behaves structurally as a natural protein, (ii) confirms the design of the radical site, (iii) reveals that the ligated phenol forms an inter helical hydrogen bond to glutamate-13 (phenol oxygen/carboxyl oxygen distance 3.2 ± 0.5 Å), and (iv) suggests a proton-transfer pathway from the buried phenol OH (average solvent accessible surface area of 3 ± 5%) via glutamate-13 (average solvent accessible surface area of the carboxyl oxygens 37 ± 18%) to the bulk solvent. A square-wave voltammetry analysis of 2-mercaptophenol-?3C further demonstrates: (v) that the phenol oxidation-reduction cycle is reversible, (vi) that formal reduction potentials can be obtained, and (vii) that the phenol-O• state is long lived with an estimated lifetime of ? 180 milliseconds. These properties make 2-mercaptophenol-?3C a unique system to characterize phenol-based proton-coupled electron transfer in a low dielectric and structured protein environment. PMID:23373469

  6. 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

  7. Determination of carbonyl groups in oxidatively modified proteins by reduction with tritiated sodium borohydride

    SciTech Connect

    Lenz, A.G.; Costabel, U.; Shaltiel, S.; Levine, R.L. )

    1989-03-01

    Oxidatively modified proteins have been implicated in a variety of physiologic and pathologic processes. Oxidative modification typically causes inactivation of enzymes and also the introduction of carbonyl groups into amino acid side chains of the protein. We describe a method to quantify oxidatively modified proteins through reduction of these carbonyl groups with tritiated borohydride. The technique was applied to purified, oxidatively modified glutamine synthetase and to bronchoalveolar lavage fluid from dogs and from humans. Since the protein content of lung lavage fluid is low, a very sensitive method was required to measure the oxidized residues. Reduction of the carbonyl group generated during oxidation of proteins with tritiated borohydride provided excellent sensitivity. Incorporation of tritium was directly proportional to the amount of protein with a range from 10 to 1000 micrograms. Should moieties other than amino acids be labeled, they are easily removed by rapid benchtop hydrolysis of the protein followed by chromatography on Dowex 50.

  8. 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.

  9. Superior Catalytic Activity of Electrochemically Reduced Graphene Oxide Supported Iron Phthalocyanines toward Oxygen Reduction Reaction.

    PubMed

    Liu, Dong; Long, Yi-Tao

    2015-11-01

    Structure and surface properties of supporting materials are of great importance for the catalytic performance of the catalysts. Herein, we prepared the iron phthalocyanine (FePc) functionalized electrochemically reduced graphene oxide (ERGO) by the electrochemical reduction of FePc/GO. The resultant FePc/ERGO exhibits higher catalytic activity toward ORR than that of FePc/graphene. More importantly, the onset potential for ORR at FePc/ERGO positively shifts by 45 mV compared with commercial Pt/C in alkaline media. Besides, FePc/ERGO displays enhanced durability and selectivity toward ORR. The superior catalytic performance of FePc/ERGO for ORR are ascribed to the self-supported structure of ERGO, uniformly morphology and size of FePc nanoparticles. PMID:26477473

  10. 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...

  11. Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts.

    PubMed

    Chen, Yihong; Kanan, Matthew W

    2012-02-01

    The importance of tin oxide (SnO(x)) to the efficiency of CO(2) reduction on Sn was evaluated by comparing the activity of Sn electrodes that had been subjected to different pre-electrolysis treatments. In aqueous NaHCO(3) solution saturated with CO(2), a Sn electrode with a native SnO(x) layer exhibited potential-dependent CO(2) reduction activity consistent with previously reported activity. In contrast, an electrode etched to expose fresh Sn(0) surface exhibited higher overall current densities but almost exclusive H(2) evolution over the entire 0.5 V range of potentials examined. Subsequently, a thin-film catalyst was prepared by simultaneous electrodeposition of Sn(0) and SnO(x) on a Ti electrode. This catalyst exhibited up to 8-fold higher partial current density and 4-fold higher faradaic efficiency for CO(2) reduction than a Sn electrode with a native SnO(x) layer. Our results implicate the participation of SnO(x) in the CO(2) reduction pathway on Sn electrodes and suggest that metal/metal oxide composite materials are promising catalysts for sustainable fuel synthesis. PMID:22239243

  12. SmCo5/Fe nanocomposites synthesized from reductive annealing of oxide nanoparticles

    E-print Network

    Liu, J. Ping

    SmCo5/Fe nanocomposites synthesized from reductive annealing of oxide nanoparticles Yanglong Hou nanocomposites SmCo5/Fex x=0­2.9 are synthesized by a simultaneous calcium reduction of Sm­Co­O and Fe3O4 SmCo-based exchange-spring nanocomposites for high performance permanent magnet applications. © 2007

  13. 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. erial measurements of Eh and groundwater analyses we...

  14. 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...

  15. 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.

  16. Effect of magnetic field on reduction of nickel oxide

    NASA Technical Reports Server (NTRS)

    Rowe, M. W.; Fanick, R.; Jewett, J.; Rowe, J. D.

    1976-01-01

    Results of observations recorded during constant temperature reduction of NiO, a paramagnetic substance, to Ni, a ferromagnetic element, are presented. The application of a large magnetic field (4,200 oersted) does not result in an acceleration of the reduction rate. To explain earlier observations that 500- and 1,400-oersted magnetic fields increase the reduction rate of iron ore which contains hematite (Fe2O3), Peters (1973) had suggested that thermodynamics theory could predict the acceleration in reaction rate when product and reactant species differ widely in their magnetic properties.

  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. 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.

  19. 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 reduction. The Michaelis-Menten K{sub m} values of 71 {+-} 22 m{sup 2}/L for hematite and 50 {+-} 16 m{sup 2}/L for goethite were calculated as a function of surface area of the two insoluble minerals. V{sub max} was determined to be 123 {+-} 14 and 156 {+-} 13 nmol Fe(II)/min/mg of TM protein for hematite and goethite, respectively. These values are consistent with in vivo rates of reduction reported in the literature. These observations are consistent with our conclusion that the enzymatic reduction of mineral oxides is an effective probe that will allow elucidation of molecular chemistry of the membrane-mineral interface where electron transfer occurs.

  20. 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.

  1. 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 utilization of dissolved Fe(II) as an energy source is not likely to take place. PMID:25915449

  2. Exfoliation of graphite oxide in propylene carbonate and thermal reduction of the resulting graphene oxide platelets.

    PubMed

    Zhu, Yanwu; Stoller, Meryl D; Cai, Weiwei; Velamakanni, Aruna; Piner, Richard D; Chen, David; Ruoff, Rodney S

    2010-02-23

    Graphite oxide was exfoliated and dispersed in propylene carbonate (PC) by bath sonication. Heating the graphene oxide suspensions at 150 degrees C significantly reduced the graphene oxide platelets; paper samples comprising such reduced graphene oxide platelets had an electrical conductivity of 5230 S/m. By adding tetraethylammonium tetrafluoroborate (TEA BF(4)) to the reduced graphene oxide/PC slurry and making a two-cell ultracapacitor, specific capacitance values of about 120 F/g were obtained. PMID:20112929

  3. 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.

  4. 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.

  5. 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.

  6. 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}.

  7. 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 also serve as the terminal reductases for soluble forms of Fe(III). Although our understanding of the Mtr pathway is still far from complete, it is the best characterized microbial pathway used for extracellular electron exchange. Characterizations of the Mtr pathway have made significant contributions to the molecular understanding of microbial reduction of Fe(III) oxides.

  8. 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 detailed understanding of the vertical and longitudinal distribution of microbial taxa throughout CP. These studies will provide insight into the operation of the microbial Fe redox cycle, demonstrating how genomic properties relate to and control geochemical conditions with depth and distance in a Fe-rich, neutral pH geothermal environment.

  9. Technetium reduction in sediments of a shallow aquifer exhibiting dissimilatory iron reduction potential

    E-print Network

    Roden, Eric E.

    Technetium reduction in sediments of a shallow aquifer exhibiting dissimilatory iron reduction of the Federation of European Microbiological Societies. Keywords: Technetium; Iron reduction; Sediments; Bioremediation 1. Introduction Technetium (99 Tc) is a long-lived (t1=2 ¼ 2:13 Â 105 years) nuclear fission

  10. 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

  11. 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.

  12. Nitrogen loss through anaerobic ammonium oxidation coupled to iron reduction from paddy soils in a chronosequence.

    PubMed

    Ding, Long-Jun; An, Xin-Li; Li, Shun; Zhang, Gan-Lin; Zhu, Yong-Guan

    2014-09-16

    Anaerobic ammonium oxidation coupled to iron(III) reduction (termed Feammox) with dinitrogen, nitrite, or nitrate as the end-product is a recently discovered process of nitrogen cycling. However, Feammox has not been described in paddy soils, which are rich in iron(III) oxides and subjected to intensive nitrogen fertilization. Here, evidence for Feammox in a paddy soil chronosequence with a gradient of microbially reducible iron(III) levels was obtained in Southern China using (15)N-labeled ammonium-based isotopic tracing and acetylene inhibition techniques. Our study demonstrated the occurrence of Feammox in the chronosequence, and direct dinitrogen production was shown to be the dominant Feammox pathway. Within the chronosequence, three paddy soils with higher microbially reducible iron(III) levels had higher Feammox rates (ranged from 0.17 to 0.59 mg N kg(-1) d(-1)) compared to an uncultivated soil (0.04 mg N kg(-1) d(-1)). It is estimated that a loss of 7.8-61 kg N ha(-1) year(-1) is associated with Feammox in the examined paddy soils. Overall, we discover that rice cultivation could enrich microbially reducible iron(III), accelerate Feammox reaction and thus fuel nitrogen loss from soils, and suggest that Feammox could be a potentially important pathway for nitrogen loss in paddy soils. PMID:25158120

  13. Breakdown into nanoscale of graphene oxide: Confined hot spot atomic reduction and fragmentation

    PubMed Central

    Gonçalves, Gil; Vila, Mercedes; Bdikin, Igor; de Andrés, Alicia; Emami, Nazanin; Ferreira, Rute A. S.; Carlos, Luís D.; Grácio, José; Marques, Paula A. A. P.

    2014-01-01

    Nano-graphene oxide (nano-GO) is a new class of carbon based materials being proposed for biomedical applications due to its small size, intrinsic optical properties, large specific surface area, and easy to functionalize. To fully exploit nano-GO properties, a reproducible method for its production is of utmost importance. Herein we report, the study of the sequential fracture of GO sheets onto nano-GO with controllable lateral width, by a simple, and reproducible method based on a mechanism that we describe as a confined hot spot atomic fragmentation/reduction of GO promoted by ultrasonication. The chemical and structural changes on GO structure during the breakage were monitored by XPS, FTIR, Raman and HRTEM. We found that GO sheets starts breaking from the defects region and in a second phase through the disruption of carbon bonds while still maintaining crystalline carbon domains. The breaking of GO is accompanied by its own reduction, essentially by the elimination of carboxylic and carbonyl functional groups. Photoluminescence and photothermal studies using this nano-GO are also presented highlighting the potential of this nanomaterial as a unique imaging/therapy platform. PMID:25339424

  14. Distribution Behavior of Phosphorus and Metallization of Iron Oxide in Carbothermic Reduction of High-Phosphorus Iron Ore

    NASA Astrophysics Data System (ADS)

    Cha, Ji-Whoe; Kim, Dong-Yuk; Jung, Sung-Mo

    2015-10-01

    Distribution behavior of phosphorus and metallization of iron ore in the carbothermic reduction of high-phosphorus iron ore were investigated. Reduction degree of the iron oxide was evaluated by quadruple mass spectrometry connected to thermogravimetric analysis. The distribution of some elements including phosphorus was examined by electron probe micro-analyzer mapping analyses. The reduction behavior of high-phosphorus iron ore was evaluated as a function of reduction temperature, C/O molar ratio, and CaO addition. High reduction temperature accelerated the reduction of both iron oxide and hydroxylapatite, and high C/O molar ratio also promotes both of them. Those were contradictory to the targets of higher reduction degree of iron oxide and of lower one of hydroxylapatite. It was confirmed that appropriate amount of CaO addition could enhance the reduction of iron oxide, and regulate the reduction of hydroxylapatite.

  15. 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.

  16. 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.

  17. Bystanding F+ Oxidants Enable Selective Reductive Elimination from High-Valent Metal Centers in Catalysis

    PubMed Central

    Engle, Keary M.; Mei, Tian-Sheng; Wang, Xisheng; Yu, Jin-Quan

    2011-01-01

    Reductive elimination from partially or completely oxidized metal centers is a vital step in a myriad of carbon–carbon and carbon–heteroatom bond–forming reactions. One strategy for promoting otherwise challenging reductive elimination reactions is to oxidize the metal center using a two-electron oxidant (i.e., from M(n) to M(n+2)). However, many of the commonly used oxidants for this type of transformation contain oxygen, nitrogen, or halogen moieties that are subsequently capable of participating in reductive elimination, leading to a mixture of products. This minireview examines an emerging solution to this widespread problem in organometallic chemistry, the use of bystanding F+ oxidants, and describes recent applications in Pd(II)/Pd(IV) and Au(I)/Au(III) catalysis. We then briefly discuss a rare example in which one-electron oxidants have been shown to promote selective reductive elimination in Pd(II)-catalyzed C–H functionalization, which we view as a promising future directing in the field. PMID:21264991

  18. Reduction in the onset time of breakaway oxidation on Zircaloy cladding ruptured under simulated LOCA conditions

    NASA Astrophysics Data System (ADS)

    Yamato, Masaaki; Nagase, Fumihisa; Amaya, Masaki

    2014-02-01

    Breakaway oxidation, which is characterized by sudden increases in oxidation rate and significant hydrogen absorption after longer exposure in high-temperature steam, was examined for the ballooned and ruptured cladding. Short test rods with PWR-type Zircaloy-4 cladding were heated in steam and oxidized at 1273 K for periods from 1200 to 3600 s after ballooning and rupture. The breakaway oxidation was observed after more than 1500 s in the ruptured cladding whereas it was observed after more than 3600 s in the non-ruptured cladding at this temperature. The cause of the reduction in the onset time of breakaway oxidation was investigated with changing possible influential parameters. The onset time of breakaway oxidation was reduced only in the case where thick and porous oxide was formed on the inner surface of the cladding after rupture. Results of the parametric experiments suggest that the tensile stress in the circumferential direction generated by the thick oxide film formed on the inner surface is a main cause of the reduction in the onset time of breakaway oxidation.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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 ?m) 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

  4. Nitrogen oxide reduction strategies for compression ignition engines

    NASA Astrophysics Data System (ADS)

    Chapman, Elana M.

    2008-05-01

    The scope of this investigation is to explore strategies to reduce NOx emissions from compression ignition engines. Two methods are presented in this collection of studies: (1) NOx reduction accomplished through a change in fuel formulation, specifically through a change in the saturated fuel carbon chains of biodiesel; and (2) NOx reduction accomplished through a mixed mode combustion process utilizing a fumigated fuel and a pilot injection of diesel fuel. In the first study, a light duty diesel engine was used to investigate the change in saturation of a biodiesel fuel and its impact on NOx emissions. Previous studies have shown that a reduction in the iodine value of a biodiesel fuel produces a reduction in NOx emissions. The iodine value of the fuel is reduced through the saturation of the C18 molecules via hydrogenation of biodiesel fuel. Experiments were performed at several speeds and loads without exhaust gas recirculation (EGR), and a NOx reduction with the hydrogenated diesel fuel was observed. For all the modes studied, the NOx emission was higher for the biodiesel and lower for the hydrogenated biodiesel in comparison to the ultra low sulfur diesel (ULSD) fuel. Results from the calculation of the adiabatic flame temperature shows that the results could be explained by the difference in adiabatic flame temperature of the fuel, thus influencing the prompt NOx contribution in addition to the thermal contribution. Since the adiabatic flame temperatures are similar for the hydrogenated biodiesel and the ULSD, yet the NOx reduction with the hydrogenated biodiesel is much lower than the ULSD levels, another explanation for the reduction is suggested: the additional prompt NOx contribution from the change in fuel chemistry. The second study investigated the NOx reductions which could be achieved with a mixed mode combustion process utilizing a fumigated fuel and a pilot injection of diesel fuel. In this research, the fumigated fuel was dimethyl ether (DME) and DME/Methane blends, while the pilot injection fuel was ULSD. Several sets of experiments were performed to study the ignition of the fumigated fuel, and its impact on the NOx emissions. In the first set of experiments, the DME concentration was spanned over a range of 15 to 44% energy equivalent of the total fuel requirement. An approximately 20% reduction in NOx emissions was observed up to 35% DME energy equivalent. As the energy equivalent increased above 35%, the NOx emissions began to increase with the increase in the peak of the high temperature heat release (HTHR). While the NOx emissions decreased, there was also a significant shift in the NO to NO2 conversion for all DME fumigation test conditions in comparison to the baseline diesel cases. For 25% DME energy equivalent, the injection timing of the pilot diesel was retarded and a reduction in the NOx emissions was observed. The low temperature heat release (LTHR) and the HTHR remained constant in magnitude and timing while the injection timing of the pilot diesel was retarded. The peak pressure for the premixed and diffusion portions merged, with increasing premixed DME combustion. With retarded injection timing, NOx reduction occurred as a result of the decrease in the bulk cylinder temperature and in the combustion duration before cylinder quenching from the exhaust stroke. In the second set of experiments, the intake air temperature was increased to study the impact on NOx and the mixed mode combustion process. While the amount of DME residual in the exhaust decreased along with the total hydrocarbon and CO emissions, the NOx emissions increased with increasing bulk cylinder temperature. For the speed and load used in this experiment, there was enough fuel and compression to combust most of the fuel, yet not enough to complete the combustion of the unburned hydrocarbons and CO. While air heating shifted the stoichiometry of the fuel and air mixture by reducing the density of air, the heating led to increased NOx with reduction in the NO to NO2 conversion. This may indicate that the system was above

  5. Oxidation Potential, Not Crystal Structure, Controls the Oxidation State of Iron in Perovskite

    NASA Astrophysics Data System (ADS)

    Panero, W. R.; Pigott, J. S.; Watson, H. C.; Scharenberg, M.; Green, H. W.; McComb, D. W.; Williams, R. E.

    2013-12-01

    The mantle's oxidation state has broad implications on the state and evolution of the earth's interior. The relatively high oxidation potential of the upper mantle is such that iron is predominantly Fe2+ with small amounts of Fe3+ . Fe3+ is more stable than Fe2+ in the dominant lower mantle mineral, perovskite, despite the fact that the effect of pressure is to reduce the oxidizing potential of a system. It is therefore suggested that iron undergoes a disproportionation reaction of 3Fe2+ =2Fe3+ +Fe0 , controlled by the crystallography instead of oxidation potential. We crystallized synthetic enstatite glass with 5% Al2O3, 14% FeO, and 3% Fe2O3 in the laser-heated diamond anvil cell at 25-63 GPa and 1700-2800 K. We find that for temperatures <2200 K, the sample crystallizes to only perovskite, while at higher temperatures, the sample crystallizes to perovskite and stishovite as evident in x-ray diffraction, with 5-50 nm iron precipitates on grain boundaries. The precipitates have small amounts of dissolved oxygen, but are Mg- and Al- free. We interpret that the stishovite is forming due to the oxidation of the ferric iron to ferrous iron according to (Mg2+,Al3+)(Fe3+,Si4+)O3 +SiO2 + Fe0 while the lower-temperature samples crystallizing as approximately (Mg2+ Fe2+ Al3+ )(Fe3+ Al3+ Si4+ )O3. We observe 2.8(2) Å3 volume expansion of the perovskite and a 28(2) GPa decrease in compressibility of the perovskite relative to the perovskite forming at lower temperature, consistent with the proposed compositions of the perovskites. As the increased temperature increases the oxidation potential of the system, we suggest that the oxidation state of iron in perovskite is dependent on oxidation potential as opposed to perovskite's crystal structure. Transmission Electron Microscopy (TEM) coupled with Electron Energy Loss Spectroscopy (EELS) show iron precipitation on grain boundaries supporting the conclusion. We present a discussion of the results and implications for core formation and lower mantle dynamics.

  6. Reductive Dissolution of Iron Oxides and Iron-Rich Clays Enhanced by Sulfate-Reducing Bacteria

    NASA Astrophysics Data System (ADS)

    Zhang, C. L.

    2003-12-01

    Iron oxides and iron-rich clays are abundant in low-temperature sedimentary environments where sulfate-reducing bacteria are also present. This study summarizes our research on reductive dissolution of ferrihydrite, goethite, hematite, magnetite, and a nontronite clay by Desulfovibrio spp. strain G-20 and strain G-11. The goal was twofold: (1) to understand the enzymatic processes of iron reduction by sulfate-reducing bacteria (SRB) using iron as the sole electron acceptor and (2) to determine whether iron reduction from the oxides and clays could be enhanced by biogenic H2S through an enzymatic process during sulfate reduction. In the iron-oxide experiments without sulfate, iron reduction by G-20 averaged about 4.5% of total iron for ferrihydrite, goethite, and hematite. The reduction of magnetite, however, was about threefold higher (13.3%). The maximum biomass of G-20 gained during iron reduction was also highest in the magnetite culture, suggesting that reduction of magnetite may have stimulated the growth of G-20. In the presence of sulfate, iron reduction was dramatically enhanced in all cultures (>70%). In inorganic experiments using Na2S, less than 4% total iron was reduced from goethite or hematite and about 19% was reduced from magnetite. The enhanced reduction of iron during sulfate reduction may have resulted from enzymatic activity of the SRB or through the chelation of solids with organic acids and other organic molecules. Transmission electron microscopy (TEM) showed shortened and thinned goethite and hematite crystals during sulfate and iron reduction. The magnetite crystals, on the other hand, were disintegrated extensively. For the nontronite experiments using G-11, iron reduction from the clay was about 10% of total structural Fe(III) in the absence of sulfate but reached 29% in the presence of sulfate. Abiotic iron reduction using Na2S, on the other hand, was ca. 7.5% of total structural Fe(III). Analyses of TEM and X-ray diffraction revealed significant changes in structure and composition of the clay during its dissolution by G-11. Overall, this study demonstrates that sulfate-reducing bacteria can dramatically enhance the dissolution of iron oxides and iron-rich clays, thus accelerating the transformation of these minerals in sulfate-rich environments.

  7. Superior catalysts for selective catalytic reduction of nitric oxide. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Li, W.B.; Yang, R.T.

    1995-12-01

    Efforts continued towards the synthesis of new pillared clay catalysts for the selective catalytic reduction of nitric oxide by ammonia. The possibility of utilizing hydrocarbons was also investigated.

  8. Holographic patterning of graphene-oxide films by light-driven reduction

    E-print Network

    Orabona, Emanuele; Longo, Angela; Carotenuto, Gianfranco; Nicolais, Luigi; Maddalena, Pasquale

    2014-01-01

    We report on the patterning and reduction of graphene-oxide films by holographic lithography. Light reduction can be used to engineer low-cost graphene-based devices by performing a local conversion of insulating oxide into the conductive graphene. In this work, computer generated holograms have been exploited to realize complex graphene patterns in a single shot, differently from serial laser writing or mask-based photolithographic processes. The technique has been further improved by achieving speckle noise reduction: submicron and diffraction-limited features have been obtained. In addition we have also demonstrated that the gray-scale lithography capability can be used to obtain different reduction levels in a single exposure.

  9. Holographic patterning of graphene-oxide films by light-driven reduction.

    PubMed

    Orabona, E; Ambrosio, A; Longo, A; Carotenuto, G; Nicolais, L; Maddalena, P

    2014-07-15

    We report on the patterning and reduction of graphene-oxide films by holographic lithography. Light reduction can be used to engineer low-cost graphene-based devices by performing a local conversion of insulating oxide into the conductive graphene. In this work, computer-generated holograms have been exploited to realize complex graphene patterns in a single shot, different from serial laser writing or mask-based photolithographic processes. The technique has been further improved by achieving speckle noise reduction: submicron and diffraction-limited features have been obtained. In addition we have also demonstrated that the gray-scale lithography capability can be used to obtain different reduction levels in a single exposure. PMID:25121702

  10. 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.

  11. Voltammetry of a flavocytochrome c(3): the lowest potential heme modulates fumarate reduction rates.

    PubMed Central

    Butt, J N; Thornton, J; Richardson, D J; Dobbin, P S

    2000-01-01

    Iron-induced flavocytochrome c(3), Ifc(3), from Shewanella frigidimarina NCIMB400, derivatized with a 2-pyridyl disulfide label, self-assembles on gold electrodes as a functional array whose fumarate reductase activity as viewed by direct electrochemistry is indistinguishable from that of Ifc(3) adsorbed on gold or graphite electrodes. The enhanced stability of the labeled protein's array permits analysis at a rotating electrode and limiting catalytic currents fit well to a Michaelis-Menten description of enzyme kinetics with K(M) = 56 +/- 20 microM, pH 7.5, comparable to that obtained in solution assays. At fumarate concentrations above 145 microM cyclic voltammetry shows the catalytic response to contain two features. The position and width of the lower potential component centered on -290 mV and corresponding to a one-electron wave implicates the oxidation state of the lowest potential heme of Ifc(3) as a defining feature in the mechanism of fumarate reduction at high turnover rates. We propose the operation of dual pathways for electron transfer to the active site of Ifc(3) with the lowest potential heme acting as an electron relay on one of these pathways. PMID:10653813

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

    DOEpatents

    Pence, Dallas T. (Idaho Falls, ID); Thomas, Thomas R. (Idaho Falls, ID)

    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.

  13. Oxidation and Reduction of the 5-(2’-Deoxyuridinyl)methyl Radical**

    PubMed Central

    Lin, Gengjie; Li, Lei

    2013-01-01

    Sleeping beauty: The 5-(2’-Deoxyuridinyl) methyl radical 1 is a key intermediate in the thymine oxidative reaction mediated by reactive oxygen species. Evidence is presented that 1 is prone to both oxidation and reduction reactions at the absence of O2. These results question the current paradigm and suggest that the redox chemistry of 1, which has been largely overlooked in the past, may play a major role in determining the fate of 1. PMID:23589226

  14. Ascorbic acid potentiates the substrate-specific inhibition of mixed-function oxidation and the stimulation of NADPH oxidation caused by paraquat.

    PubMed

    Montgomery, M R; Shamblin, P B

    1984-01-01

    Paraquat inhibits the in vitro hepatic microsomal metabolism of both ethylmorphine and aniline. Inclusion of ascorbate with paraquat in the incubations did not alter the paraquat effect on ethylmorphine N-demethylase activity but potentiated the inhibition of aniline p-hydroxylase activity. Ascorbate alone was without effect on the metabolism of either substrate. Paraquat stimulated the hepatic microsomal oxidation of nicotinamide adenine dinucleotide phosphate (NADPH) equally in the absence of mixed-function oxidase (MFO) substrates or in the presence of ethylmorphine; in the presence of aniline the rate of NADPH oxidation was significantly greater. Also, in the presence of aniline, ascorbate potentiated the paraquat-induced NADPH oxidation, while it was ineffective with paraquat on NADPH oxidation in the presence of ethylmorphine or in the absence of substrates for the microsomal MFO system. The potentiated inhibition of aniline metabolism, concomitant with the potentiated stimulation of NADPH oxidation, was consistent whether liver microsomal fractions were prepared from control rats or from animals induced with phenobarbital. Investigation of possible influences on NADPH cytochrome c reductase activity was precluded by the rapid nonenzymatic reduction of cytochrome c by ascorbate. The paraquat-ascorbate redox couple would not reduce cytochrome P-450. These data suggest that a paraquat interaction with the active microsomal MFO enzyme system plays a role in the depletion of cellular NADPH stores that occurs after paraquat administration in vivo. This mechanism may play a significant role in the development of paraquat toxicity and in the potentiated toxicity observed with ascorbate and paraquat. PMID:6716512

  15. Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis.

    PubMed

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

    2011-08-31

    Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(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 L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) 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 m(2)/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*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (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 [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (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, CO(2) 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 conditions was also demonstrated by comparing PXRD patterns before and after catalysis. This work illustrates the potential of combining molecular catalysts and MOF structures in developing highly active heterogeneous catalysts for solar energy utilization. PMID:21780787

  16. Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

    NASA Astrophysics Data System (ADS)

    Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

    2015-12-01

    Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

  17. 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.

  18. 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.

  19. Liquid-phase and solid-phase microwave irradiations for reduction of graphite oxide

    NASA Astrophysics Data System (ADS)

    Zhao, Na; Wen, Chen-Yu; Zhang, David Wei; Wu, Dong-Ping; Zhang, Zhi-Bin; Zhang, Shi-Li

    2014-12-01

    In this paper, two microwave irradiation methods: (i) liquid-phase microwave irradiation (MWI) reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and (ii) solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis, and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygen-containing functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I(D)/I(G) ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.

  20. 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

  1. Measurement of the Md3+/Md2+ reduction potential studied with flow electrolytic chromatography.

    PubMed

    Toyoshima, Atsushi; Li, Zijie; Asai, Masato; Sato, Nozomi; Sato, Tetsuya K; Kikuchi, Takahiro; Kaneya, Yusuke; Kitatsuji, Yoshihiro; Tsukada, Kazuaki; Nagame, Yuichiro; Schädel, Matthias; Ooe, Kazuhiro; Kasamatsu, Yoshitaka; Shinohara, Atsushi; Haba, Hiromitsu; Even, Julia

    2013-11-01

    The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By application of the appropriate potentials on the chromatography column, the more stable Md(3+) is reduced to Md(2+). The reduction potential of the Md(3+) + e(-) ? Md(2+) couple was determined to be -0.16 ± 0.05 V versus a normal hydrogen electrode. PMID:24116851

  2. 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.

  3. 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.

  4. Mechanism of oxygen reduction reaction on transition metal oxide catalysts for high temperature fuel cells

    E-print Network

    La O', Gerardo Jose Cordova

    2008-01-01

    The solid oxide fuel cell (SOFC) with its high energy conversion efficiency, low emissions, silent operation and its ability to utilize commercial fuels has the potential to create a large impact on the energy landscape. ...

  5. 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

  6. Oxidatively generated DNA lesions as potential biomarkers of in vivo oxidative stress.

    PubMed

    Ravanat, J-L; Cadet, J; Douki, T

    2012-07-01

    During the last three decades there was an increasing interest for developing biomarkers of oxidative stress. Therefore, efforts have been made to develop sensitive methods aimed at measuring cellular levels of oxidatively generated DNA lesions. Initially, most attention had focused on 8-oxo-7,8-dihydro-2'- deoxyguanosine (8-oxodGuo) probably because reliable analytical methods (mostly HPLC coupled to electrochemical detection) were available since mid-eighties to detect that lesion at the cellular level. With the recent development of more versatile analytical (using mass spectrometric detection) and biochemical assays (such as the comet assay) efforts are currently made to measure simultaneously several DNA lesions. The main degradation pathways of the four main pyrimidine (thymine, cytosine) and purine (adenine, guanine) bases mediated by hydroxyl radical (•OH), one-electron oxidants and singlet oxygen (1O2) have been also studied in detail and results indicate that other DNA modification than 8-oxodGuo could represent suitable biomarkers of oxidative stress. In this review article, the main oxidative degradation products of DNA will be presented together with their mechanisms of formation. Then the developed methods aimed at measuring cellular levels of oxidatively generated DNA lesions will be critically reviewed based on their specificity, versatility and sensitivity. Illustration of the powerfulness of the described methods will be demonstrated using quantification of DNA lesions in cells exposed to ionizing radiations. In addition, recent work highlighting the possible formation of complex DNA lesions will be reported and commented regarding the possibility of using such complex damage as potential biomarkers of oxidative stress. PMID:22292434

  7. Effect of reduction treatment on microstructure and mechanical properties of fluorite oxides

    NASA Astrophysics Data System (ADS)

    Wang, Yanli

    Ceria based materials because of their high ionic conductivity at low temperatures are potential candidates as the electrolyte component in the new generation of low temperature solid oxide fuel cells (SOFCs). The effects of operation conditions in SOFCs on microstructure and mechanical integrity of ceria-based materials are evaluated in this research. Pure ceria and gadolinium doped ceria (GDC) were selected to perform this investigation. The state-of-art electrolyte material, yttria-stabilized zirconia (YSZ), was also studied for comparison purposes. The samples were heat treated at 800°C under various oxygen partial pressures ( PO2 s) until equilibrium was reached. The defect concentrations were conserved to room temperature by fast cooling. The crystal structure and the lattice parameter were evaluated by the x-ray diffraction method. Microstructural evaluations and fractographic analyses were conducted using electron microscopy techniques. The intrinsic elastic modulus was evaluated using nanoindentation techniques. The bulk elastic modulus and fracture strength were measured using the four-point-bend testing method and fracture toughness was evaluated using chevron-notched Brazilian disc samples loaded under the mode I condition. The result of this study revealed that microcracks were formed during the reduction heat treatment in ceria and GDC when the PO2 was lower than 10-19 atm. It was also found that ceria samples upon cooling experienced phase transformation that led to the formation of several ordered pseudo-cubic phases. The intrinsic elastic modulus of both ceria and GDC decreased drastically when heat treated at very low PO2 s while the effect was insignificant in YSZ. These results correlate well with our theoretical modeling. Further analysis suggests that an increase in the point defect concentration weakens the attractive forces between atoms. The degradation of bulk elastic modulus of ceria was more pronounced at low PO2 s due to the presence of microcracks caused by the reduction treatments. The results on fracture properties of ceria showed that the flexural strength decreased significantly after reduction in very low PO2 s; however, in contrast, fracture toughness was increased by 30--40% when the PO2 was decreased to the range of 10-20--10-22 atm. Fractographic studies showed that the microcracks developed during reduction treatment are responsible for the decreased strength. In this dissertation, the enhancement in toughness was explained by crack deflection and microcrack toughening mechanisms.

  8. 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.

  9. NITRIC OXIDE REDUCTION IN KILNS AND HEATERS BY FUEL/AIR STAGING

    EPA Science Inventory

    The paper gives results of studies of the applicability and effectiveness of fuel/air staging (variously called In-furnace NOx Reduction, reburning, or biased firing) in controlling nitrogen oxide (NOx) emissions from refinery process heaters and cement kilns. The studies were co...

  10. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide

    E-print Network

    Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide Sasha, and by electrical conductivity measurements. Ó 2007 Elsevier Ltd. All rights reserved. 1. Introduction Graphite, thermal, and electrical properties of graphite [4]. These excellent properties may be relevant

  11. Electrolytic Reduction of Spent Oxide Fuel – Bench-Scale Test Results

    SciTech Connect

    S. D. Herrmann; S. X. Li; M. F. Simpson

    2005-10-01

    A series of tests were performed to demonstrate the electrolytic reduction of spent light water reactor fuel at bench-scale in a hot cell at the Idaho National Laboratory Materials and Fuels Complex (formerly Argonne National Laboratory - West). The process involves the conversion of oxide fuel to metal by electrolytic means, which would then enable subsequent separation and recovery of actinides via existing electrometallurgical technologies, i.e., electrorefining. Four electrolytic reduction runs were performed at bench scale using ~500 ml of molten LiCl -- 1 wt% Li2O electrolyte at 650 ºC. In each run, ~50 g of crushed spent oxide fuel was loaded into a permeable stainless steel basket and immersed into the electrolyte as the cathode. A spiral wound platinum wire was immersed into the electrolyte as the anode. When a controlled electric current was conducted through the anode and cathode, the oxide fuel was reduced to metal in the basket and oxygen gas was evolved at the anode. Salt samples were extracted before and after each electrolytic reduction run and analyzed for fuel and fission product constituents. The fuel baskets following each run were sectioned and sampled, revealing an extent of uranium oxide reduction in excess of 98%.

  12. 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.

  13. Size-induced Shifts in Oxidation-Reduction Phase Equilibria in

    E-print Network

    Size-induced Shifts in Oxidation- Reduction Phase Equilibria in N h T iti M t l O id Frontiers. A general formulation of the effect of particle size on chemical equilibria among solid phases energies of different polymorphs, causing size driven thermodynamic crossovers in phase stability

  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. 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...

  16. 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%.

  17. 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…

  18. The potential of synthetic indolylquinoline derivatives for A? aggregation reduction by chemical chaperone activity.

    PubMed

    Chang, Kuo-Hsuan; Chiu, Ya-Jen; Chen, Shu-Ling; Huang, Chen-Hsiang; Lin, Chih-Hsin; Lin, Te-Hsien; Lee, Chi-Mei; Ramesh, Chintakunta; Wu, Chung-Hsin; Huang, Chin-Chang; Fung, Hon-Chung; Chen, Yi-Chun; Lin, Jung-Yaw; Yao, Ching-Fa; Huang, Hei-Jen; Lee-Chen, Guey-Jen; Lee, Ming-Chung; Hsieh-Li, Hsiu Mei

    2016-02-01

    Alzheimer's disease (AD) is the most prevalent form of dementia associated with progressive cognitive decline and memory loss. Extracellular ?-amyloid (A?) is a major constituent of senile plaques, one of the pathological hallmarks of AD. A? deposition causes neuronal death via a number of possible mechanisms such as increasing oxidative stress. Therefore therapeutic approaches to identify novel A? aggregate reducers could be effective for AD treatment. Using a Trx-His-A? biochemical assay, we screened 11 synthetic indolylquinoline compounds, and found NC009-1, -2, -6 and -7 displaying potential to reduce A? aggregation. Treating Tet-On A?-GFP 293 cells with these compounds reduced A? aggregation and reactive oxygen species. These compounds also promoted neurite outgrowth in Tet-On A?-GFP SH-SY5Y cells. Furthermore, treatment with above compounds improved neuronal cell viability, neurite outgrowth, and synaptophysin expression level in mouse hippocampal primary culture under oligomeric A?-induced cytotoxicity. Moreover, the tested NC009-1 significantly ameliorated A?-induced inhibition of hippocampal long-term potentiation in mouse hippocampal slices. Our results demonstrate how synthetic indolylquinoline compounds are likely to work as chemical chaperones in A?-aggregation reduction and neuroprotection, providing insight into the possible applications of indolylquinoline compounds in AD treatment. PMID:26362358

  19. Limitation of Acetylene Reduction (Nitrogen Fixation) by Photosynthesis in Soybean Having Low Water Potentials 1

    PubMed Central

    Huang, Chi-Ying; Boyer, John S.; Vanderhoef, Larry N.

    1975-01-01

    The role of photosynthesis and transpiration in the desiccation-induced inhibition of acetylene reduction (nitrogen fixation) was investigated in soybean (Glycine max [L.] Merr. var. Beeson) using an apparatus that permitted simultaneous measurements of acetylene reduction, net photosynthesis, and transpiration. The inhibition of acetylene reduction caused by low water potentials and their aftereffects could be reproduced by depriving shoots of atmospheric CO2 even though the soil remained at water potentials that should have favored rapid acetylene reduction. The inhibition of acetylene reduction at low water potentials could be partially reversed by exposing the shoots to high CO2 concentrations. When transpiration was varied independently of photosynthesis and dark respiration in plants having high water potentials, no effects on acetylene reduction could be observed. There was no correlation between transpiration and acetylene reduction in the CO2 experiments. Therefore, the correlation that was observed between transpiration and acetylene reduction during desiccation was fortuitous. We conclude that the inhibition of shoot photosynthesis accounted for the inhibition of nodule acetylene reduction at low water potentials. PMID:16659277

  20. 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

  1. 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.

  2. A one-step, solvothermal reduction method for producing reduced graphene oxide dispersions in organic solvents.

    PubMed

    Dubin, Sergey; Gilje, Scott; Wang, Kan; Tung, Vincent C; Cha, Kitty; Hall, Anthony S; Farrar, Jabari; Varshneya, Rupal; Yang, Yang; Kaner, Richard B

    2010-07-27

    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 degrees 2theta (3.4 A), 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

  3. 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° 2? (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

  4. Post-fabrication, in situ laser reduction of graphene oxide devices

    NASA Astrophysics Data System (ADS)

    Petridis, C.; Lin, Y.-H.; Savva, K.; Eda, G.; Kymakis, E.; Anthopoulos, T. D.; Stratakis, E.

    2013-03-01

    We report on post-fabrication, in situ, laser induced reduction of graphene oxide (GO) field effect transistors. Our one-step method is efficient, fast, and elevates the conductivity of GO transistor channels by two orders of magnitude. Compared to other reduction techniques, it is facile and simple since it does not require any stringent experimental conditions. Most importantly, we show here that it can be applied for, in situ, post-fabrication reduction of GO devices without compromising any of its components. The physical properties of the laser-reduced graphene oxide were assessed by micro-Raman and X-ray photoelectron spectroscopy analysis and the electrical properties by electric field effect measurements. The application of this technique in other graphene-based optoelectronic devices, especially those fabricated on inexpensive and temperature sensitive flexible substrates such as plastic, is envisaged.

  5. Synthesis of graphene nanosheets via oxalic acid-induced chemical reduction of exfoliated graphite oxide

    SciTech Connect

    Song, Peng; Zhang, Xiao-Yan; Sun, Mingxun; Cui, Xiao-Li; Lin, Yuehe

    2012-02-01

    Preparing high-quality graphene through reduction of graphene oxide (GO) by oxalic acid is demonstrated in this paper. Transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction and Raman spectrometry were taken to confirm the reduction of GO and the formation of graphene under these mild conditions. Thermogravimetric analysis and conductivity measurements further testify the excellent thermal stability and conductivity of the obtained graphene. A possible mechanism for the reduction process was also proposed. Furthermore, a Pt-graphene composite was fabricated on a glassy carbon electrode and excellent electrocatalytic activity towards methanol oxidation was observed. With advantages of low toxicity, simple purification process and high quality of the product, oxalic acid provides a feasible route to prepare graphene from GO under mild conditions, thus facilitating the use of graphene-based materials for large-scale applications.

  6. 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

  7. 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??m, 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

  8. 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

  9. 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 73-131nm and a width of 5-6nm. 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

  10. 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.

  11. Staged reaction kinetics and characteristics of iron oxide direct reduction by carbon

    NASA Astrophysics Data System (ADS)

    Wei, Ru-fei; Cang, Da-qiang; Zhang, Ling-ling; Bai, Yuan-yuan

    2015-10-01

    Staged reduction kinetics and characteristics of iron oxide direct reduction by carbon were studied in this work. The characteristics were investigated by simultaneous thermogravimetric analysis, X-ray diffraction (XRD), and quadrupole mass spectrometry. The kinetics parameters of the reduction stages were obtained by isoconversional (model-free) methods. Three stages in the reduction are Fe2O3?Fe3O4, Fe3O4?FeO, and FeO?Fe, which start at 912 K, 1255 K, and 1397 K, respectively. The CO content in the evolved gas is lower than the CO2 content in the Fe2O3?Fe3O4 stage but is substantially greater than the CO2 contents in the Fe3O4?FeO and FeO?Fe stages, where gasification starts at approximately 1205 K. The activation energy ( E) of the three stages are 126-309 kJ/mol, 628 kJ/mol, and 648 kJ/mol, respectively. The restrictive step of the total reduction is FeO?Fe. If the rate of the total reduction is to be improved, the rate of the FeO?Fe reduction should be improved first. The activation energy of the first stage is much lower than those of the latter two stages because of carbon gasification. Carbon gasification and Fe x O y reduction by CO, which are the restrictive step in the last two stages, require further study.

  12. Reduction of sidewall defect induced leakage currents by the use of nitrided field oxides in silicon selective epitaxial growth isolation

    E-print Network

    Bashir, Rashid

    to conventional recessed local oxidation of silicon LOCOS or shallow trench isolation STI , SEG of silicon of the oxide isolation region as shown in Fig. 2 a . For the case of MOSFETs, however, as shown in Fig. 2 bReduction of sidewall defect induced leakage currents by the use of nitrided field oxides

  13. In situ reduction and reoxidation of a solid oxide fuel cell anode in an environmental Q. Jeangros1

    E-print Network

    Dunin-Borkowski, Rafal E.

    of yttria stabilized zirconia (YSZ) and nickel oxide (NiO). NiO is reduced into metallic nickel during procedure is important as it influences the anode support conductivity and strength. Oxidation of the nickelIn situ reduction and reoxidation of a solid oxide fuel cell anode in an environmental TEM Q

  14. Rheostat Re-Wired: Alternative Hypotheses for the Control of Thioredoxin Reduction Potentials

    E-print Network

    Bewley, Kathryn D.

    Thioredoxins are small soluble proteins that contain a redox-active disulfide (CXXC). These disulfides are tuned to oxidizing or reducing potentials depending on the function of the thioredoxin within the cell. The mechanism ...

  15. Energy Use Reduction Potential in the Beet Sugar Industry 

    E-print Network

    Barron, T. S.; Heist, J. A.

    1984-01-01

    0 L CD ..... J_ ..~..~.~ 0 0 III 0 w ::> QPa U'l o : 'B o L a: 0 w c f- U'l III :--flY~.s ~T ,,; 10 20 30 1i0 ELECTRICITY USE (KWH/TON SLICEl FIGURE 5 493 ESL-IE-84-04-84 Proceedings from the Sixth Annual Industrial Energy... stream_source_info ESL-IE-84-04-84.pdf.txt stream_content_type text/plain stream_size 18382 Content-Encoding ISO-8859-1 stream_name ESL-IE-84-04-84.pdf.txt Content-Type text/plain; charset=ISO-8859-1 ENERGY USE REDUCTION...

  16. 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.

  17. 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 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. Electronic supplementary information (ESI) available: Preparation of graphene oxide, nitrogen adsorption analysis results, FTIR spectra, TEM images and elemental mapping, TGA, XPS and supplementary electrochemical tests. See DOI: 10.1039/c5nr03089g

  18. Effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper in synthesized Fe(III) minerals and Fe-rich soils.

    PubMed

    Hu, Chaohua; Zhang, Youchi; Zhang, Lei; Luo, Wensui

    2014-04-01

    The effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper were investigated in a high concentration of sulfate with synthesized Fe(III) minerals and red earth soils rich in amorphous Fe (hydr)oxides. Batch microcosm experiments showed that red earth soil inoculated with subsurface sediments had a faster Fe(III) bioreduction rate than pure amorphous Fe(III) minerals and resulted in quicker immobilization of Cu in the aqueous fraction. Coinciding with the decrease of aqueous Cu, SO4(2-) in the inoculated red earth soil decreased acutely after incubation. The shift in the microbial community composite in the inoculated soil was analyzed through denaturing gradient gel electrophoresis. Results revealed the potential cooperative effect of microbial Fe(III) reduction and sulfate reduction on copper immobilization. After exposure to air for 144 h, more than 50% of the immobilized Cu was remobilized from the anaerobic matrices; aqueous sulfate increased significantly. Sequential extraction analysis demonstrated that the organic matter/sulfide-bound Cu increased by 52% after anaerobic incubation relative to the abiotic treatment but decreased by 32% after oxidation, indicating the generation and oxidation of Cu-sulfide coprecipitates in the inoculated red earth soil. These findings suggest that the immobilization of copper could be enhanced by mediating microbial Fe(III) reduction with sulfate reduction under anaerobic conditions. The findings have an important implication for bioremediation in Cucontaminated and Fe-rich soils, especially in acid-mine-drainage-affected sites. PMID:24448165

  19. Impurity evaluation of fused lithium chloride salt for a pilot-scale oxide reduction.

    SciTech Connect

    Eberle, C. S.; Herrmann, S. D.; King, R. W.; Engineering Division

    1999-12-01

    The inorganic and physical chemistry of reactants (e.g., impurities) produced during the reduction of spent light water reactor fuel in a hot cell has been analyzed. Two source terms were identified that influence the composition and quantity of these impurities in the salt matrix. One source comes from the reduction process, which occurs between the fuel and the Li/LiCl salt matrix, and the other from chemical reactions that occur between the hot cell atmosphere and the salt matrix. The spent-fuel-oxide chemistry and energy of formation for the reactants were evaluated. Most of the rare-earth-oxide reactions were not thermodynamically feasible with molten lithium, except when nitrogen was present during the reduction process. A model of the reaction at a vapor-liquid interface was developed and applied to the pilot-scale oxide reduction device design. A predominance diagram for the Li-O-N reactions was constructed to determine the possible reactions during operation of the device, and from these results, the mass accumulation was determined from hot cell conditions.

  20. Reduction mechanism of hydroxyl group from graphene oxide with and without -NH2 agent

    NASA Astrophysics Data System (ADS)

    Jin, Mengting; Jiao, N.; Zhang, C. X.; Xiao, H. P.; Zhang, K. W.; Sun, L. Z.

    2015-11-01

    First-principles calculations have been performed to investigate the reduction mechanism of hydroxyl group from graphene oxide (GO). We find that when the system is negatively charged the hydroxy group can be directly desorbed from GO due to the Coulomb repulsion derived from the extra charge accumulation between hydroxyl group and GO. And then we choose ammonia as the reducing agent for the hydroxyl group of GO. The results of substitution energy indicates that the -NH2 group can easily substitute the -OH. Such substitution maybe a viable reduction process because -NH2 group can also be easily reduced when the system is negatively charged. Both reduction mechanisms proposed in our present work involve negatively charged state which provide hint to understand the GO reduction in experiment.

  1. 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.

  2. 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.

  3. 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.

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

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.

    1973-01-01

    The effectiveness of hydrogen, carbon and hydrogen-carbon in reducing NiO, Cr2O3, mixed NiO-Cr2O3 and oxidized Ni-20Cr was evaluated by thermogravimetry. 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, hydrogen-carbon and partially by carbon alone. The results indicate that nickel and carbon promote the reduction of Cr2O3.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. [Concentration of macroergic phosphates and oxidative potential of skeletal muscles].

    PubMed

    Nemirovskaia, T L; Shenkman, B S; Mazin, M G; Koshelev, V B; Maevski?, E I; Grishina, E

    2000-01-01

    It is known that a long-duration decline of high-energy phosphate (HP) level in skeletal muscles, induced by administration of beta-guanidinpropionic acid (beta-GPA), is followed by an increase in mitochondrial enzyme activities (MEA). The same increase in MEA was observed in the course of physical exercise training. Under gravitational inloading decrease in MEA and increase in the level of high-energy phosphates occurred. If changes in (HP) level are believed to trigger the alterations in MEA, the increase in high-energy phosphate levels in muscles is to lead to a decline in MEA as well. The present work was purposed to reveal if changes in HP level under different contractile activity levels may be associated with changes in oxidative potential in the skeletal muscles. PMID:10709257

  11. Sludge reduction potential of the activated sludge process by integrating an oligochaete reactor.

    PubMed

    Wei, Yuansong; Wang, Yawei; Guo, Xuesong; Liu, Junxin

    2009-04-15

    An oligochaete reactor linked to an integrated oxidation ditch with vertical cycle (IODVC) was used to investigate the sludge reduction potential induced by worms. The presence of Tubificidae was observed in the worm reactor throughout the operational period after its inoculation, and Tubificidae was occasionally found in the IODVC. Free-swimming worms, Aeolosoma hemprichi, Nais elinguis, and Aulophorus furcatus, were found in both the IODVC and the worm reactor, but A. hemprichi was dominant. A. hemprichi reached its maximum, 322 and 339 Aeolosoma/mL mixed liquor on day 49 in the worm reactor and the IODVC, respectively. The presence of oligochaetes or the integration of worm reactor with the IODVC had little effect on sludge yield, but the worm growth was helpful for improving sludge settling characteristics. The average sludge yield and sludge volume index (SVI) in the IODVC were 0.33 kgSS/kgCOD(removed) and 78 mL/g, respectively. The worm presence had little impact on effluent quality of the IODVC, but it caused phosphorus release into the effluent. The average COD, NH(4)(+)-N, and SS concentrations in the effluent of the IODVC were 49.06, 12.82, and 58.25 mg/L, respectively. No total nitrogen (TN) release into the effluent of the IODVC occurred. PMID:18667270

  12. 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. In general, scores were highest for samples collected on the northeast side of the facility.

  13. 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.

  14. Going Wireless: Fe(III) Oxide Reduction without Pili by Geobacter sulfurreducens Strain JS-1

    PubMed Central

    Shrestha, Pravin Malla; Snoeyenbos-West, Oona L.; Franks, Ashley E.; Nevin, Kelly P.; Lovley, Derek R.

    2014-01-01

    Previous studies have suggested that the conductive pili of Geobacter sulfurreducens are essential for extracellular electron transfer to Fe(III) oxides and for optimal long-range electron transport through current-producing biofilms. The KN400 strain of G. sulfurreducens reduces poorly crystalline Fe(III) oxide more rapidly than the more extensively studied DL-1 strain. Deletion of the gene encoding PilA, the structural pilin protein, in strain KN400 inhibited Fe(III) oxide reduction. However, low rates of Fe(III) reduction were detected after extended incubation (>30 days) in the presence of Fe(III) oxide. After seven consecutive transfers, the PilA-deficient strain adapted to reduce Fe(III) oxide as fast as the wild type. Microarray, whole-genome resequencing, proteomic, and gene deletion studies indicated that this adaptation was associated with the production of larger amounts of the c-type cytochrome PgcA, which was released into the culture medium. It is proposed that the extracellular cytochrome acts as an electron shuttle, promoting electron transfer from the outer cell surface to Fe(III) oxides. The adapted PilA-deficient strain competed well with the wild-type strain when both were grown together on Fe(III) oxide. However, when 50% of the culture medium was replaced with fresh medium every 3 days, the wild-type strain outcompeted the adapted strain. A possible explanation for this is that the necessity to produce additional PgcA, to replace the PgcA being continually removed, put the adapted strain at a competitive disadvantage, similar to the apparent selection against electron shuttle-producing Fe(III) reducers in many anaerobic soils and sediments. Despite increased extracellular cytochrome production, the adapted PilA-deficient strain produced low levels of current, consistent with the concept that long-range electron transport through G. sulfurreducens biofilms is more effective via pili. PMID:24814783

  15. Inhibition by sulfide of nitric and nitrous oxide reduction by denitrifying Pseudomonas fluorescens

    SciTech Connect

    Sorensen, J.; Tiedje, J.M.; Firestone, R.B.

    1980-01-01

    The influence of low redox potentials and H/sub 2/S on NO and N/sub 2/O reduction by resting cells of dentrifying Pseudomonas fluorescens was studied. Hydrogen sulfide and Ti(III) were added to achieve redox potentials near -200 mv. The control without reductant had a redox potential near +200 mv. Production of /sup 13/No, (/sup 13/N)N/sub 2/O, and (/sup 13/N)N/sub 2/ from /sup 13/NO/sub 3//sup -/ and /sup 13/NO/sub 2//sup -/ was followed. Total gas production was similar for all three treatments. The accumulation of /sup 13/NO was most significant in the presence of sulfide. A parallel control with autoclaved cells indicated that the /sup 13/NO production was largely biological. The sulfide inhibition was more dramatic at the level of N/sub 2/O reduction; (/sup 13/N)NO/sub 2/ became the major product instead of (/sup 13/N)N/sub 2/, the dominant product when either no reductant or Ti(III) was present. The results indicate that the specific action of sulfide rather than the low redox potential caused a partial inhibition of NO reduction and a strong inhibition of N/sub 2/O reduction in denitrifying cells.

  16. Layer-by-layer motif hybridization: nanoporous nickel oxide flakes wrapped into graphene oxide sheets toward enhanced oxygen reduction reaction.

    PubMed

    Zakaria, Mohamed B; Malgras, Victor; Takei, Toshiaki; Li, Cuiling; Yamauchi, Yusuke

    2015-11-01

    Herein we report a novel strategy involving the hybridization of nanoporous NiO flakes with graphene oxide (GO) sheets. The as-prepared flake-like nickel cyano-bridged coordination polymers (NiCNNi) are hybridized with GO sheets and thermally treated in air, so the organic materials can be removed without affecting the integrity of the parent GO sheets. Thus, the layer-by-layer construction followed by a thermal treatment can produce a new hybrid nanoporous material consisting of NiO and GO. The obtained hybrid material exhibits an efficient catalytic activity and stability for the oxygen reduction reaction (ORR). PMID:26411422

  17. Ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium in two US Great Basin hot springs with abundant ammonia-oxidizing archaea.

    PubMed

    Dodsworth, Jeremy A; Hungate, Bruce A; Hedlund, Brian P

    2011-08-01

    Many thermophiles catalyse free energy-yielding redox reactions involving nitrogenous compounds; however, little is known about these processes in natural thermal environments. Rates of ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were measured in source water and sediments of two ? 80°C springs in the US Great Basin. Ammonia oxidation and denitrification occurred mainly in sediments. Ammonia oxidation rates measured using (15)N-NO(3)(-) pool dilution ranged from 5.5 ± 0.8 to 8.6 ± 0.9 nmol N g(-1) h(-1) and were unaffected or only mildly stimulated by amendment with NH(4) Cl. Denitrification rates measured using acetylene block ranged from 15.8 ± 0.7 to 51 ± 12 nmol N g(-1) h(-1) and were stimulated by amendment with NO(3)(-) and complex organic compounds. The DNRA rate in one spring sediment measured using an (15)N-NO(3)(-) tracer was 315 ± 48 nmol N g(-1) h(-1). Both springs harboured distinct planktonic and sediment microbial communities. Close relatives of the autotrophic, ammonia-oxidizing archaeon 'Candidatus Nitrosocaldus yellowstonii' represented the most abundant OTU in both spring sediments by 16S rRNA gene pyrotag analysis. Quantitative PCR (qPCR) indicated that 'Ca. N. yellowstonii'amoA and 16S rRNA genes were present at 3.5-3.9 × 10(8) and 6.4-9.0 × 10(8) copies g(-1) sediment. Potential denitrifiers included members of the Aquificales and Thermales. Thermus spp. comprised <1% of 16S rRNA gene pyrotags in both sediments and qPCR for T. thermophilus narG revealed sediment populations of 1.3-1.7 × 10(6) copies g(-1) sediment. These data indicate a highly active nitrogen cycle (N-cycle) in these springs and suggest that ammonia oxidation may be a major source of energy fuelling primary production. PMID:21631688

  18. 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.

  19. Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

    DOEpatents

    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.

  20. Reductive mobilization of oxide-bound metals: The role of reductant capacity and reductant reactivity in determining mobilization rates in soils and sediments

    SciTech Connect

    Stone, A.T.

    1990-10-01

    We seek to identify environmental factors that exert a decisive influence on the mobilization of oxide-bound toxic metals in soils, sediments, and aquifers. Our objective is to examine how the complexant and reductant characteristics of organic compounds found in contaminated aquatic environments influence this mobilization process. Laboratory experiments begin by allowing toxic metals (Co, Ni, Pb, Cu) to adsorb onto host oxide phases (particulate MnO{sub 2} and FeOOH) for a period of 17 hours. Dissolved metal concentrations are then monitored after the addition of low molecular weight reference compounds (such as oxalate, malonate, and citrate) or natural organic matter. A variety of phenomena have been observed. Oxalate, for example, acts as a complexant at pH 6, solubilizing adsorbed Cu and Ni while leaving the MnO{sub 2} host phase intact. At pH 4, oxalate acts as both a complexant and reductant, causing solubilization of adsorbed Cu and Ni, and the MnO{sub 2} host phase. When toxic metals are equilibrated with NOM from the Great Dismal Swamp before MnO{sub 2} addition, the extent of adsorption is less than in NOM-free suspensions. As the host MnO{sub 2} phase is dissolved, the extent of toxic metal adsorption changes little. 4 refs., 8 figs., 1 tab.

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

    PubMed

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

    2012-02-22

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

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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 links diet and health. PMID:25803049

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

    PubMed

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

    2015-09-21

    A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-?) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-? proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-? undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 ? Mn3O4 ? MnO. PMID:26239114

  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. 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.

  11. Consequence of one-electron oxidation and one-electron reduction for aniline.

    PubMed

    Raczy?ska, Ewa D; St?pniewski, Tomasz M; Kolczy?ska, Katarzyna

    2011-12-01

    Quantum-chemical calculations were performed for all possible isomers of neutral aniline and its redox forms, and intramolecular proton-transfer (prototropy) accompanied by ?-electron delocalization was analyzed. One-electron oxidation (PhNH(2) - e???[PhNH(2)](+•)) has no important effect on tautomeric preferences. The enamine tautomer is preferred for oxidized aniline similarly as for the neutral molecule. Dramatical changes take place when proceeding from neutral to reduced aniline. One-electron reduction (PhNH(2)?+?e???[PhNH(2)](-•)) favors the imine tautomer. Independently on the state of oxidation, ?- and n-electrons are more delocalized for the enamine than imine tautomers. The change of the tautomeric preferences for reduced aniline may partially explain the origin of the CH tautomers for reduced nucleobases (cytosine, adenine, and guanine). PMID:21369938

  12. 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}.

  13. Biogenic iron mineralization accompanying the dissimilatory reduction of hydrous ferric oxide by a groundwater bacterium

    NASA Astrophysics Data System (ADS)

    Fredrickson, James K.; Zachara, John M.; Kennedy, David W.; Dong, Hailang; Onstott, Tullis C.; Hinman, Nancy W.; Li, Shu-mei

    1998-10-01

    Dissimilatory iron-reducing bacteria (DIRB) couple the oxidation of organic matter or H 2 to the reduction of iron oxides. The factors controlling the rate and extent of these reduction reactions and the resulting solid phases are complex and poorly understood. Batch experiments were conducted with amorphous hydrous ferric oxide (HFO) and the DIRB Shewanella putrefaciens, strain CN32, in well-defined aqueous solutions to investigate the reduction of HFO and formation of biogenic Fe(II) minerals. Lactate-HFO solutions buffered with either bicarbonate or 1,4-piperazinediethanesulfonic acid (PIPES) containing various combinations of phosphate and anthraquinone-2,6-disulfonate (AQDS), were inoculated with S. putrefaciens CN32. AQDS, a humic acid analog that can be reduced to dihydroanthraquinone by CN32, was included because of its ability to function as an electron shuttle during microbial iron reduction and as an indicator of pe. Iron reduction was measured with time, and the resulting solids were analyzed by X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (SAED). In HCO 3- buffered medium with AQDS, HFO was rapidly and extensively reduced, and the resulting solids were dominated by ferrous carbonate (siderite). Ferrous phosphate (vivianite) was also present in HCO 3- medium containing P, and fine-grained magnetite was present as a minor phase in HCO 3- medium with or without P. In the PIPES-buffered medium, the rate and extent of reduction was strongly influenced by AQDS and P. With AQDS, HFO was rapidly converted to highly crystalline magnetite whereas in its absence, magnetite mineralization was slower and the final material less crystalline. In PIPES with both P and AQDS, a green rust type compound [Fe (6-x)IIFe xIII(OH) 12] x+[(A 2-) x/2 · yH 2O] x- was the dominant solid phase formed; in the absence of AQDS a poorly crystalline product was observed. The measured pe and nature of the solids identified were consistent with thermodynamic considerations. The composition of aqueous media in which microbial iron reduction occurred strongly impacted the rate and extent of iron reduction and the nature of the reduced solids. This, in turn, can provide a feedback control mechanism on microbial metabolism. Hence, in sediments where geochemical conditions promote magnetite formation, two-thirds of the Fe(III) will be sequestered in a form that may not be available for anaerobic bacterial respiration.

  14. Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process

    DOEpatents

    Gardner, Timothy J. (Albuquerque, NM); Lott, Stephen E. (Edgewood, NM); Lockwood, Steven J. (Albuquerque, NM); McLaughlin, Linda I. (Albuquerque, NM)

    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.

  15. Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments

    PubMed Central

    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 terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

  16. 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 terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

  17. 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.

  18. 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 ?m (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

  19. 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 parallel also a further OP detection method. PMID:25787944

  20. 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 typically lower than those in real-world driving.

  1. 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 OM-related quality parameters of water. Finally, study of relationships between the different OM forms, climate parameters (temperature, raw water flow, rainfall) and coagulant amounts showeds that each OM form was specifically linked to these parameters. In particular, we were able to pinpoint one of the five forms that was most associated with the water flow, and also the most flocculated by the coagulant. In conclusion, this work demonstrates that our fluorescence analyzer helps to get improved knowledge of OM behavior during potabilization process. Five different OM forms were identified and their respective evolution was characterized. Furthermore, we evidenced a potential use of a compact and small-size analyzer to monitor water purification steps through simultaneous prediction of quality parameters related to OM content.

  2. 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.

  3. 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 wire mesh accelerated the Li2O dissolution rate by more than a factor of six.

  4. 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 ?V) 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 consideration decreased by a factor of two or more, including the zero coherence function value. The similar result was obtained for another basic low-frequency electro-neurophysiological rhythm delta (f = 0.5 - 3.9 Hz, A = 20 ?V). The usual coherence function values from the interval [0.3, 0.8] were being registered, typically, about 48 hours after the magnetic storm end. The result about decreasing of the coherence of the brain low frequency bioelectric oscillations under a magnetic storm influence was obtained by two methods: 1) comparison of the time series of bioelectric oscillations of a given person without a magnetic storm and under its influence; 2) comparison of two sets of time series of oscillations: a) the set A of time series measured without a magnetic storm and b) the set B of time series measured under its influence, regardless to an individual. Surely, the total number of the EEGs available for the investigation by the set’s approach, i.e. without personification, is more than the number of the EEGs available by the individual approach because there were ones investigated without a magnetic storm only as well as ones investigated under its influence only. By the EEG measurements with closed or open eyes, but without a functional load on the brain in the form of the proof-reading test, a distinctive decrease of the coherence function was not observed during a magnetic storm as well as for pairs of points from other parts of the head (see above) or other rhythms.

  5. Shuttle to Shuttle 2: Subsystem weight reduction potential (estimated 1992 technology readiness date)

    NASA Technical Reports Server (NTRS)

    Macconochie, Ian O.

    1988-01-01

    The objective of this study was to make estimates of the weight savings that might be realized on all the subsystems on an advanced rocket-powered shuttle (designated Shuttle 2) by using advanced technologies having a projected maturity date of 1992. The current Shuttle with external tank was used as a baseline from which to make the estimates of weight savings on each subsystem. The subsystems with the greatest potential for weight reduction are the body shell and the thermal protection system. For the body shell, a reduction of 5.2 percent in the weight of the vehicle at main engine cutoff is projected through the application of new technologies, and an additional configuration-based reduction of 5 percent is projected through simplification of body shape. A reduction of 5 percent is projected for the thermal protection system through experience with the current Space Shuttle and the potential for reducing thermal protection system thicknesses in selected areas. Main propellant tanks are expected to increase slightly in weight. The main propulsion system is also projected to increase in weight because of the requirement to operate engines at derated power levels in order to accommodate one-engine-out capability. The projections for weight reductions through improvements in the remaining subsystems are relatively small. By summing all the technology factors, a projected reduction of 16 percent in the vehicle weight at main engine cutoff is obtained. By summarizing the configurational factors, a potential reduction of 12 percent in vehicle weight is obtained.

  6. Reduction of Salmonella enterica on alfalfa seeds with acidic electrolyzed oxidizing water and enhanced uptake of acidic electrolyzed oxidizing water into seeds by gas exchange.

    PubMed

    Stan, Silvia D; Daeschel, Mark A

    2003-11-01

    Alfalfa sprouts have been implicated in several salmonellosis outbreaks in recent years. The disinfectant effects of acidic electrolyzed oxidizing (EO) water against Salmonella enterica both in an aqueous system and on artificially contaminated alfalfa seeds were determined. The optimum ratio of seeds to EO water was determined in order to maximize the antimicrobial effect of EO water. Seeds were combined with EO water at ratios (wt/vol) of 1:4, 1:10, 1:20, 1:40, and 1:100, and the characteristics of EO water (pH, oxidation reduction potential [ORP], and free chlorine concentration) were determined. When the ratio of seeds to EO water was increased from 1:4 to 1:100, the pH decreased from 3.82 to 2.63, while the ORP increased from +455 to +1,073 mV. EO water (with a pH of 2.54 to 2.38 and an ORP of +1,083 to +1,092 mV) exhibited strong potential for the inactivation of S. enterica in an aqueous system (producing a reduction of at least 6.6 log CFU/ml). Treatment of artificially contaminated alfalfa seeds with EO water at a seed-to-EO water ratio of 1:100 for 15 and 60 min significantly reduced Salmonella populations by 2.04 and 1.96 log CFU/g, respectively (P < 0.05), while a Butterfield's buffer wash decreased Salmonella populations by 0.18 and 0.23 log CFU/g, respectively. After treatment, EO water was Salmonella negative by enrichment with or without neutralization. Germination of seeds was not significantly affected (P > 0.05) by treatment for up to 60 min in electrolyzed water. The uptake of liquid into the seeds was influenced by the internal gas composition (air, N2, or O2) of seeds before the liquid was added. PMID:14627277

  7. Chemical and Enzymatic Transformations of Nimesulide to GSH Conjugates through Reductive and Oxidative Mechanisms.

    PubMed

    Zhou, Lei; Pang, Xiaoyan; Xie, Cen; Zhong, Dafang; Chen, Xiaoyan

    2015-12-21

    Nimesulide (NIM) is a nonsteroidal anti-inflammatory drug, and clinical treatment with NIM has been associated with severe hepatotoxicity. The bioactivation of nitro-reduced NIM (NIM-NH2), a major NIM metabolite, has been thought to be responsible for the hepatotoxicity of NIM. However, we found that NIM-NH2 did not induce toxic effects in primary rat hepatocytes. This study aimed to investigate other bioactivation pathways of NIM and evaluate their association with hepatotoxicity. After incubating NIM with NADPH- and GSH-supplemented human or rat liver microsomes, we identified two types of GSH conjugates: one was derived from the attachment of GSH to NIM-NH2 (NIM-NH2-GSH) and the other one was derived from a quinone-imine intermediate (NIM-OH-GSH). NIM-NH2-GSH was generated not only by the oxidative activation of NIM-NH2 but also from the reductive activation of NIM. Both NADPH and GSH could act as reducing agents. Moreover, aldehyde oxidase also participated in the reductive activation of NIM. NIM-OH-GSH was generated mainly from NIM via epoxidation with CYP1A2 as the main catalyzing enzyme. NIM was toxic to both primary human and rat hepatocytes, with IC50 values of 213 and 40 ?M, respectively. Inhibition of the oxidative and reductive activation of NIM by the nonspecific CYP inhibitor 1-aminobenzotriazole and selective aldehyde oxidase inhibitor estradiol did not protect the cells from NIM-mediated toxicity. Moreover, pretreating cells with l-buthionine-sulfoximine (a GSH depletor) did not affect the cytotoxicity of NIM. These results suggested that oxidative and reductive activation of NIM did not cause the hepatotoxicity and that the parent drug concentration was associated with the cytotoxicity. PMID:26524229

  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. A New Mechanism in Electrochemical Process for Arsenic Oxidation: Production of H2O2 from Anodic O2 Reduction on the Cathode under Automatically Developed Alkaline Conditions.

    PubMed

    Qian, Ao; Yuan, Songhu; Zhang, Peng; Tong, Man

    2015-05-01

    Electrochemical cathodes are often used to reduce contaminants or produce oxidizing substances (i.e., H2O2). Alkaline conditions develop automatically around the cathode in electrochemical processes, and O2 diffuses onto the cathode easily. However, limited attention is paid to contaminant transformation by the reactive species produced on the cathode under oxic and alkaline conditions due to the inapplicability of pH for Fenton reaction. In this study, a new oxidation mechanism on the cathode is presented for contaminant transformation under automatically developed alkaline conditions. In an electrochemical sand column, 6.67 ?M As(III) was oxidized by 36% when it passed through the cathode under the conditions of 30 mA current, an initial pH of 7.5 and a flow rate of 2 mL/min. Under the alkaline conditions (pH 10.0-11.0) that developed automatically around the cathode, the reduction potential of As(III) decreased greatly, allowing a pronounced oxidation by the small quantities of H2O2 produced from O2 reduction on the cathode. As(III) oxidation was further increased by the presence of soil pore water and groundwater solutes of HCO3-, Ca2+, Mg2+ and humic acid. The new oxidation mechanism found for the cathode under localized alkaline conditions supplements the fundamentals of contaminant transformation in electrochemical processes. PMID:25853500

  10. Natural Oxidant Demand Variability, Potential Controls, and Implications for in Situ, Oxidation-Based Remediation of Contaminated Groundwater

    NASA Astrophysics Data System (ADS)

    Dettmer, A.; Cruz, S.; Dungan, B.; Holguin, F. O.; Ulery, A. L.; Hunter, B.; Carroll, K. C.

    2014-12-01

    Naturally occurring reduced species associated with subsurface materials can impose a significant natural oxidant demand (NOD), which is the bulk consumption of oxidants by soil water, minerals, and organic matter. Although injection of oxidants has been used for chemical transformation of organic contaminants, NOD represents a challenge for the in-situ delivery of oxidants as a remediation alternative. Co-injection of complexation agents with oxidants has been proposed to facilitate the delivery of oxidants for in situ chemical oxidation remediation of contaminated groundwater. This study investigates variability of NOD for different oxidants and sediments. The effect of the addition of various complexation agents, including EDTA, tween 80, hydroxypropyl-beta-cyclodextrin (HPCD), humic acid, and four generations of poly(amidoamine) (PAMAM) dendrimers, on the NOD was also examined. NOD was measured for a clay loam (collected from Air Force Plant 44 in Tucson, AZ). Varying amounts of biosolids were mixed with subsamples of the clay loam to create three additional reference soils in order to study the effect of organic matter and other soil characteristics on the NOD. Bench-scale laboratory experiments were conducted to determine the NOD for various oxidants, using the four soils, and replicated with and without various delivery agents. Measured NOD showed variability for each soil and oxidant composition. Additionally, significant differences were observed in NOD with the addition of delivery agents. The results support the elucidation of potential controls over NOD and have implications for in situ, oxidation-based remediation of contaminated groundwater.

  11. INFRARED PROPERTIES OF SOLID TITANIUM OXIDES: EXPLORING POTENTIAL PRIMARY DUST CONDENSATES

    E-print Network

    Kerschbaum, Franz

    INFRARED PROPERTIES OF SOLID TITANIUM OXIDES: EXPLORING POTENTIAL PRIMARY DUST CONDENSATES Th), titanium oxides are considered--together with calcium and aluminium oxides--as candidates for the very condensates. Of course, titanium is rather rare according to its mean cosmic elemen- tal abundance, which is 2

  12. ORGANIC SOIL OXIDATION POTENTIAL DUE TO PERIODIC FLOOD AND DRAINAGE DEPTH UNDER SUGARCANE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Organic soils in the Everglades Agricultural Area (EAA) are oxidizing due to aerobic microbial activity resulting in soil subsidence. Flooding helps control oxidation but may reduce crop yields. The purpose of this study was to determine organic matter oxidation potential in the upper 15 cm of soil ...

  13. OXIDATION POTENTIALS OF SOIL ORGANIC MATTER IN HISTOSOLS UNDER DIFFERENT TILLAGE METHODS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soils in the Everglades Agricultural Area (EAA) of south Florida, USA are subsiding due primarily to oxidation by aerobic microoganisms. One way to reduce oxidation of soil organic matter is through minimum tillage. An experiment was set up on a Histosol to determine the potentials for oxidation re...

  14. A synthetic leaf: the biomimetic potential of graphene oxide

    NASA Astrophysics Data System (ADS)

    Lamb, Marilla; Koch, George W.; Morgan, Eric R.; Shafer, Michael W.

    2015-03-01

    Emerging materials such as graphene oxide (GO) have micro and nano features that are functionally similar to those in plant cell walls involved in water transport. Therefore, it may now be possible to design and build biomimetic trees to lift water via mechanisms similar to those employed by trees, allowing for potential applications such as passive water pumping, filtering, and evaporative cooling. The tallest trees can raise large volumes of water to over 100 meters using only the vapor pressure gradient between their leaves and the atmosphere. This phenomenon occurs in all terrestrial plants when capillary forces generated in the microscopic pores in the cell walls of leaves are collectively applied to large diameter xylem conduits. The design of a synthetic tree that mimics these mechanisms will allow water to be moved to heights greater than is currently possible by any engineered system that does not require the use of a positive pressure pump. We are testing the suitability of membranous GO as the leaf of a synthetic tree and present an analysis in support of this design. In addition, we include results from a preliminary design using ceramics.

  15. Co-Occurrence of Nitrate Reduction and Anaerobic Oxidation of Methane in Gulf of Mexico Cold Seep Habitats

    NASA Astrophysics Data System (ADS)

    Fields, L.; Joye, S. B.

    2014-12-01

    Cold seeps are abundant in the Gulf of Mexico; they are fuelled by methane gas and hydrocarbon seepage at the seafloor and support diverse chemosynthetic microbial communities. Microorganisms form the base of the food chain at cold seeps, and high rates of anaerobic oxidation of methane (AOM) are characteristic of these methane-rich environments. While sulfate is often the electron acceptor for AOM in cold seep environments, recent evidence suggests that AOM can also be coupled to nitrate reduction. Little is known about nitrogen cycling in these habitats, though recent work indicates that denitrification is an important process in oily and gassy seep sediments. The co-occurrence of nitrate reduction and AOM suggests a potential coupling between the two processes in our study area. We used stable isotope (15N) tracer techniques to measure the capacity of Northern Gulf of Mexico cold seep sediments to reduce nitrate by denitrification and anammox. These measurements were made in surface and sub-surface sediments in conjunction with measurements of AOM, and with quantification of various geochemical and molecular characteristics. Here, we present our measurements of denitrification and anammox capacity in the context of environmental characteristics. Additionally, we examine spatial trends in the co-occurrence of AOM and nitrate reduction in these sediments.

  16. Mössbauer study of iron-based perovskite-type materials as potential catalysts for ethyl acetate oxidation

    NASA Astrophysics Data System (ADS)

    Paneva, D.; Dimitrov, M.; Velinov, N.; Kolev, H.; Kozhukharov, V.; Tsoncheva, T.; Mitov, I.

    2010-03-01

    La-Sr-Fe perovskite-type oxides were prepared by the nitrate-citrate method. The basic object of this study is layered Ruddlesden-Popper phase LaSr3Fe3O10. The phase composition and structural properties of the obtained materials are investigated by Mössbauer spectroscopy, X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and temperature programmed reduction (TPR). The preliminary catalytic tests show a high potential of these materials for volatile organic compounds (VOCs) elimination as they possess high conversion ability and selectivity to total oxidation of ethyl acetate. Catalytic performance of LaSr3Fe3O10 is depended on the stability of structure and Fe4+-oxidation state.

  17. 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.

  18. Reduction of low potential electron acceptors requires the CbcL inner membrane cytochrome of Geobacter sulfurreducens.

    PubMed

    Zacharoff, Lori; Chan, Chi Ho; Bond, Daniel R

    2016-02-01

    The respiration of metals by the bacterium Geobacter sulfurreducens requires electrons generated by metabolism to pass from the interior of the cell to electron acceptors beyond the cell membranes. The G. sulfurreducens inner membrane multiheme c-type cytochrome ImcH is required for respiration to extracellular electron acceptors with redox potentials greater than -0.1V vs. SHE, but ImcH is not essential for electron transfer to lower potential acceptors. In contrast, deletion of cbcL, encoding an inner membrane protein consisting of b-type and multiheme c-type cytochrome domains, severely affected reduction of low potential electron acceptors such as Fe(III)-oxides and electrodes poised at -0.1V vs. SHE. Catalytic cyclic voltammetry of a ?cbcL strain growing on poised electrodes revealed a 50mV positive shift in driving force required for electron transfer out of the cell. In non-catalytic conditions, low-potential peaks present in wild type biofilms were absent in ?cbcL mutants. Expression of cbcL in trans increased growth at low redox potential and restored features to cyclic voltammetry. This evidence supports a model where CbcL is a component of a second electron transfer pathway out of the G. sulfurreducens inner membrane that dominates when redox potential is at or below -0.1V vs. SHE. PMID:26407054

  19. 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 ?-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.

  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. 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 ?m 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.

  2. The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides

    PubMed Central

    Chuang, C.-H.; Wang, Y.-F.; Shao, Y.-C.; Yeh, Y.-C.; Wang, D.-Y.; Chen, C.-W.; Chiou, J. W.; Ray, Sekhar C.; Pong, W. F.; Zhang, L.; Zhu, J. F.; Guo, J. H.

    2014-01-01

    Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120–180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp2 bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and K? XES spectra shows that the overlapping ? and ?* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C K? RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the ?-region and/or in the gap between the ? and ?* levels of the GO and rGOs. Two-dimensional C K? RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the ? and ? features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG. PMID:24717290

  3. A high pressure X-ray photoelectron spectroscopy study of oxidation and reduction of Rh(100) and Rh nanoparticles

    NASA Astrophysics Data System (ADS)

    Blomberg, S.; Westerström, R.; Martin, N. M.; Lundgren, E.; Andersen, J. N.; Messing, M. E.; Gustafson, J.

    2014-10-01

    We have studied the oxidation and reduction of Rh(100) and SiO2 supported Rh particles using high pressure X-ray photoelectron spectroscopy. We show that the formation and reduction of Rh bulk oxide can be followed in situ in O2 and CO pressures in the range of 0.1 Torr. In general, the oxidation/reduction processes are similar on Rh(100) and the nanoparticles, but there are significant differences in temperature dependence. Already at a sample temperature of 140 °C, the particles show clear signs of a thin bulk oxide, while an ultra-thin so-called surface oxide covers the single crystal at the same temperature. Both of these oxide films, however, hinder further oxidation, and a thick oxide is only found at a temperature of at least 300 °C, for both samples. The reduction, in contrast, starts at a higher temperature on the particles as compared to the single crystal, but once started the particles are completely reduced at lower temperatures.

  4. 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.

  5. Thermodynamic properties of oxidation-reduction reactions of bacterial, microsomal, and mitochondrial cytochromes P-450: an entropy-enthalpy compensation effect.

    PubMed

    Huang, Y Y; Hara, T; Sligar, S; Coon, M J; Kimura, T

    1986-03-25

    An optically transparent thin-layer electrode cell with a very small volume was used for determination of the formal reduction potentials of bacterial, microsomal, and mitochondrial cytochromes P-450. At an extrapolated zero concentration of dye, the bacterial cytochrome from Pseudomonas putida catalyzing the hydroxylation of camphor and the adrenal mitochondrial cytochrome catalyzing the cholesterol side-chain cleavage reaction had formal reduction potentials of -168 and -285 mV (pH 7.5 and 25 degrees C), respectively. The oxidation-reduction potentials for the rabbit liver microsomal cytochrome P-450 induced by 3-methylcholanthrene and the mitochondrial cytochrome for steroid 11 beta-hydroxylation were found as -360 and -286 mV, respectively. Potential measurements at different temperatures allowed documentation of the standard thermodynamic parameters for cytochrome P-450 reduction for the first time. All cytochromes tested were found to have a relatively large negative entropy change upon reduction. The extent of these changes is comparable to that observed for the ferric-ferrous couple of cytochrome c. An entropy-enthalpy compensation effect was observed among the four cytochromes P-450 examined although the correlation is weaker than that observed with cytochrome c isolated from various sources. PMID:3964682

  6. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    DOEpatents

    Rieke, Peter C. (Pasco, WA); Coffey, Gregory W. (Richland, WA); Pederson, Larry R. (Kennewick, WA); Marina, Olga A. (Richland, WA); Hardy, John S. (Richland, WA); Singh, Prabhaker (Richland, WA); Thomsen, Edwin C. (Richland, WA)

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  7. Photochemically induced intramolecular six-electron reductive elimination and oxidative addition of nitric oxide by the nitridoosmate(VIII) anion.

    PubMed

    Thornley, Wyatt A; Bitterwolf, Thomas E

    2015-02-01

    UV photolysis of the nitridoosmate(VIII) anion, OsO3 N(-) , in low-temperature frozen matrices results in nitrogen-oxygen bond formation to give the Os(II) nitrosyl complex OsO2 (NO)(-) . Photolysis of the Os(II) nitrosyl product with visible wavelengths results in reversion to the parent Os(VIII) complex. Formally a six-electron reductive elimination and oxidative addition, respectively, this represents the first reported example of such an intramolecular transformation. DFT modelling of this reaction proceeds through a step-wise mechanism taking place through a side-on nitroxyl Os(VI) intermediate, OsO2 (?(2) -NO)(-) . PMID:25537499

  8. Analytic bond-order potential for atomistic simulations of zinc oxide

    E-print Network

    Nordlund, Kai

    Analytic bond-order potential for atomistic simulations of zinc oxide Paul Erhart1 , Niklas Juslin2 for zinc oxide and its elemental constituents is derived based on an analytical bond-order formalism. The model potential provides a good description of the bulk properties of various solid structures of zinc

  9. Green method to form iron oxide nanorods in orange peels for chromium(VI) reduction.

    PubMed

    López-Téllez, G; Balderas-Hernández, P; Barrera-Díaz, C E; Vilchis-Nestor, A R; Roa-Morales, G; Bilyeu, Bryan

    2013-03-01

    A green method for synthesizing iron oxide nanorods within orange peel pith has been developed. Orange peel pith functions as both a support and a reducing agent for iron ions. The nanorods were characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Results of the characterization indicate that iron is deposited on the surface of orange peel primarily in the form of iron, iron(II) oxide and magnetite. The nanoparticles grow to form nanorods in the range of 20-40 nm of diameter. The biocomposite was then tested for Cr(VI) reduction and removal from aqueous solutions, exhibiting removals as high as 96% for concentrations of 10 mg/L and 76% for 50 mg/L, which is almost 4 times the removal capacity of orange peel alone. PMID:23755691

  10. Reduction-oxidation state and protein degradation in skeletal muscle of fasted and refed rats

    NASA Technical Reports Server (NTRS)

    Fagan, Julie M.; Tischler, Marc E.

    1986-01-01

    Redox state and protein degradation were measured in isolated muscles of fasted (up to 10 d) and refed (up to 4 d) 7- to 14-wk-old rats. Protein degradation in the extensor digitorum longus muscle, but not in the soleus muscle, was greater in the fasted rats than in weight-matched muscle from fed rats. The NAD couple was more oxidized in incubated and fresh extensor digitorum longus muscles and in some incubated soleus muscles of fasted rats than in weight-matched muscle from fed rats. In the extensor digitorum longus muscle of refed or prolonged fasted rats, protein degradation was slower and the NAD couple was more reduced than in the fed state. Therefore, oxidation of the NAD couple was associated with increased muscle breakdown during fasting, whereas reduction of the NAD couple was associated with muscle conservation and deposition.

  11. Reactivity of an All-Ferrous Iron-Nitrogen Heterocubane under Reductive and Oxidative Conditions.

    PubMed

    Lichtenberg, Crispin; Prokopchuk, Demyan E; Adelhardt, Mario; Viciu, Liliana; Meyer, Karsten; Grützmacher, Hansjörg

    2015-10-26

    The reactivity of the all-ferrous FeN heterocubane [Fe4 (Ntrop)4 ] (1) with i)?Brønsted acids, ii)??-donors, iii)??-donors/?-acceptors, and iv)?one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(?3 -imido) 48 electron complex in the former case and a tetranuclear all ferric ?-oxo-?-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations. PMID:26374167

  12. Visible-light Induced Reduction of Graphene Oxide Using Plasmonic Nanoparticle.

    PubMed

    Kumar, Dinesh; Lee, Ah-Reum; Kaur, Sandeep; Lim, Dong-Kwon

    2015-01-01

    Present work demonstrates the simple, chemical free, fast, and energy efficient method to produce reduced graphene oxide (r-GO) solution at RT using visible light irradiation with plasmonic nanoparticles. The plasmonic nanoparticle is used to improve the reduction efficiency of GO. It only takes 30 min at RT by illuminating the solutions with Xe-lamp, the r-GO solutions can be obtained by completely removing gold nanoparticles through simple centrifugation step. The spherical gold nanoparticles (AuNPs) as compared to the other nanostructures is the most suitable plasmonic nanostructure for r-GO preparation. The reduced graphene oxide prepared using visible light and AuNPs was equally qualitative as chemically reduced graphene oxide, which was supported by various analytical techniques such as UV-Vis spectroscopy, Raman spectroscopy, powder XRD and XPS. The reduced graphene oxide prepared with visible light shows excellent quenching properties over the fluorescent molecules modified on ssDNA and excellent fluorescence recovery for target DNA detection. The r-GO prepared by recycled AuNPs is found to be of same quality with that of chemically reduced r-GO. The use of visible light with plasmonic nanoparticle demonstrates the good alternative method for r-GO synthesis. PMID:26436539

  13. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction.

    PubMed

    Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

    2015-01-28

    The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms. PMID:25502117

  14. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

    2015-01-01

    The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms.

  15. 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 aircraft, not only in meeting the regulatory requirements, but also in competing with aircraft of different advanced designs within this N+2 timeframe and goal framework.

  16. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    SciTech Connect

    Adams, MM; Hoarfrost, AL; Bose, A; Joye, SB; Girguis, PR

    2013-05-14

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C-2), propane (C-3), and butane (C-4) in anoxic sediments in contrast to methane (C-1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C-1-C-4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C-1-C-4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75 degrees C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C-1-C-4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C-2-C-4 alkanes. Maximum C-1-C-4 alkane oxidation rates occurred at 55 degrees C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C-3 was oxidized at the highest rate over time, then C-4, C-2, and C-1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C-2-C(4)alkanes with AOM for available oxidants and the influence on the fate of C-1 derived from these hydrothermal systems.

  17. 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 composite pellets to look into the different aspects associated with multi-layer reduction in the RHF. The reduced pellets were examined for morphology and phase distribution using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. Efforts were made to interpret the differences in the observed rates from one kind of pellet to the other on the grounds of chemical kinetics of the carbon oxidation and wustite reduction reactions and the issues of external and internal heat transport to and within the pellets. It was concluded from the experiments that in the ore containing pellets, wood-charcoal appeared to be a faster reductant than coal-char. However, in the PAH containing pellets, the reverse was found to be true. This is because of the internal heat transport limitations imposed by two factors (a) lower thermal conductivity of wood-charcoal in comparison to coal-char and (b) swelling of the PAH-Wood-Charcoal pellets during the initial heat-up stage. For the same type of reductant, hematite containing pellets were observed to reduce faster than taconite containing pellets. This is in accordance with the higher reducibility of hematite because of development of internal porosity due to cracking and fissure formation during the Fe2O3 to Fe 3O4 transformation stage. This is however, absent during the reduction of taconite, which is primarily Fe3O4. The PAH-Wood-Charcoal pellets were found to undergo significant amounts of swelling under low temperature conditions. This behavior of the PAH-Wood-Charcoal pellets of a certain layer impeded the external heat transport to the lower layer and consequently, resulted in a relatively lower reduction rate for a multi-layer bed. The volume change phenomena associated with the reduction of composites were also studied. Volume changes influence the external heat transport, especially to the lower layers of a multi-layer bed. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. Empirical correlations were developed associating the volume

  18. Preparation and Study on Nickel Oxide Reduction of Polyacrylonitrile-Based Carbon Nanofibers by Thermal Treatment.

    PubMed

    Lee, Yeong Ju; Kim, Hyun Bin; Jeun, Joon Pyo; Lee, Dae Soo; Koo, Dong Hyun; Kang, Phil Hyun

    2015-08-01

    Carbon materials containing magnetic nanopowder have been attractive in technological applications such as electrochemical capacitors and electromagnetic wave shielding. In this study, polyacrylonitrile (PAN) fibers containing nickel nanoparticles were prepared using an electrospinning method and thermal stabilization. The reduction of nickel oxide was investigated under a nitrogen atmosphere within a temperature range of 600 to 1,000 °C. Carbon nanofibers containing nickel nanoparticles were characterized by FE-SEM, EDS, XRD, TGA, and VSM. It was found that nickel nanoparticles were formed by a NiO reduction in PAN as a function of the thermal treatment. These results led to an increase in the coercivity of nanofibers and a decrease in the remanence magnetization. PMID:26369192

  19. Characterization of the thrombogenic potential of surface oxides on stainless steel for implant purposes

    NASA Astrophysics Data System (ADS)

    Shih, Chun-Che; Shih, Chun-Ming; Su, Yea-Yang; Chang, Mau-Song; Lin, Shing-Jong

    2003-12-01

    Marketed stents are manufactured from various metals and passivated with different degrees of surface oxidation. The functional surface oxides on the degree of antithrombotic potential were explored through a canine femoral extracorporeal circuit model. Related properties of these oxide films were studied by open-circuit potential, current density detected at open-circuit potential, the electrochemical impedance spectroscopy, transmission electron microscopy, Auger spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. Experimental evidences showed that blood clot weight after a 30-min follow-up was significantly lower for the stainless steel wire passivated with amorphous oxide (AO) compared to the wire passivated with polycrystalline oxide (PO) or commercial as-received wire coils (AS). Surface characterizations showed that a stable negative current density at open-circuit potential and a significant lower potential were found for the wire surface passivated with AO than for the surface passivated with PO. Time constant of AO is about 25 times larger than that of polycrystalline oxide. Significant difference in oxide grain sizes was found between PO and AO. Surface chemistries revealed by the AES and XPS spectra indicated the presence of a Cr- and oxygen-rich surface oxide for AO, and a Fe-rich and oxygen-lean surface oxide for PO. These remarkable characteristics of AO surface film might have a potential to provide for excellent antithrombotic characteristics for the 316L stainless steel stents.

  20. oxide and FeNi alloy: product dependence on the reduction ability

    NASA Astrophysics Data System (ADS)

    Cao, Jungang; Qin, Yuyang; Li, Minglun; Zhao, Shuyuan; Li, Jianjun

    2014-12-01

    Based on the sol-gel combustion method, stoichiometric Fe3+, Mn2+, Ni2+ ions and citric acid were chosen as the initial reactants for the preparation of magnetic particles. Due to the different reduction ability of metal ions, completely different magnetic products (MnFe2O4 oxide and FeNi alloy) were obtained by heating the flakes at 600 °C under nitrogen atmosphere. MnFe2O4 particles exhibit superparamagnetic behavior at room temperature, and martensitic phase transformation is observed magnetically at 125 K for FeNi alloy particles.

  1. Reversibly phototunable TiO{sub 2} photonic crystal modulated by Ag nanoparticles' oxidation/reduction

    SciTech Connect

    Liu Jian; Zhou Jinming; Ye Changqing; Li Mingzhu; Wang Jingxia; Jiang Lei; Song Yanlin

    2011-01-10

    We report a reversibly phototunable photonic crystal system whose reflectance at the stop band position can be modulated by alternating UV/visible (UV/Vis) irradiation. The phototunable system consists of Ag nanoparticles and TiO{sub 2} photonic crystal. The stop bands intensity of Ag loaded TiO{sub 2} photonic crystals were found to be dependent on the redox states of Ag nanoparticles. The quasi 'on' and 'off' states of the stop band were reversibly modulated by the Ag nanoparticles' oxidation/reduction through alternating UV/Vis light irradiation.

  2. Are the reduction and oxidation properties of nitrocompounds dissolved in water different from those produced when adsorbed on a silica surface? A DFT M05-2X computational study.

    PubMed

    Sviatenko, Liudmyla K; Isayev, Olexandr; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Leszczynski, Jerzy

    2015-05-30

    The reduction and oxidation properties of four nitrocompounds (trinitrotoluene [TNT], 2,4-dinitrotoluene, 2,4-dinitroanisole, and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one [NTO]) dissolved in water as compared with the same properties for compounds adsorbed on a silica surface were studied. To consider the influence of adsorption, cluster models were developed at the M05/tzvp level. A hydroxylated silica (001) surface was chosen to represent a key component of soil. The PCM(Pauling) and SMD solvation models were used to model water bulk influence. The following properties were analyzed: electron affinity, ionization potential, reduction Gibbs free energy, oxidation Gibbs free energy, and reduction and oxidation potentials. It was found that adsorption and solvation decrease gas phase electron affinity, ionization potential, and Gibbs free energy of reduction and oxidation, and thus, promote redox transformation of nitrocompounds. However, in case of solvation, the changes are more significant than for adsorption. This means that nitrocompounds dissolved in water are easier to transform by reduction or oxidation than adsorbed ones. Among the considered compounds, TNT was found to be the most reactive in an electron attachment process and the least reactive for an electron detachment transformation. During ionization, a deprotonation of adsorbed NTO was found to occur. PMID:25736204

  3. Nitrogen-doped and simultaneously reduced graphene oxide with superior dispersion as electrocatalysts for oxygen reduction reaction

    SciTech Connect

    Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Yoo, Sung Jong; Cho, Eun Ae; Khil, Myung-Seob; Joh, Han-Ik

    2014-11-15

    Nitrogen doped graphene oxide (Nr-GO) with properties suitable for electrocatalysts is easily synthesized using phenylhydrazine as a reductant at relatively low temperature. The reducing agent removes various oxygen functional groups bonded to graphene oxide and simultaneously dope the nitrogen atoms bonded with phenyl group all over the basal planes and edge sites of the graphene. The Nr-GO exhibits remarkable electrocatalytic activities for oxygen reduction reaction compared to the commercial carbon black and graphene oxide due to the electronic modification of the graphene structure. In addition, Nr-GO shows excellent dispersibility in various solvent due to the dopant molecules.

  4. Reduction kinetics of iron oxide pellets with H2 and CO mixtures

    NASA Astrophysics Data System (ADS)

    Zuo, Hai-bin; Wang, Cong; Dong, Jie-ji; Jiao, Ke-xin; Xu, Run-sheng

    2015-07-01

    Reduction of hematite pellets using H2-CO mixtures with a wide range of H2/CO by molar (1:0, 3:1, 1:1, 1:3, and 0:1) at different reducing temperatures (1073, 1173, and 1273 K) was conducted in a program reducing furnace. Based on an unreacted core model, the effective diffusion coefficient and reaction rate constant in several cases were determined, and then the rate-control step and transition were analyzed. In the results, the effective diffusion coefficient and reaction rate constant increase with the rise in temperature or hydrogen content. Reduction of iron oxide pellets using an H2-CO mixture is a compound control system; the reaction rate is dominated by chemical reaction at the very beginning, competition during the reduction process subsequently, and internal gas diffusion at the end. At low hydrogen content, increasing temperature takes the transition point of the rate-control step to a high reduction degree, but at high hydrogen content, the effect of temperature on the transition point weakens.

  5. Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism

    USGS Publications Warehouse

    Coates, J.D.; Councell, T.; Ellis, D.J.; Lovley, D.R.

    1998-01-01

    An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, Gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process.

  6. Temperature and pH effect on reduction of graphene oxides in aqueous solution

    NASA Astrophysics Data System (ADS)

    Tai, Guoan; Zeng, Tian; Li, Hongxiang; Liu, Jinsong; Kong, Jizhou; Lv, Fuyong

    2014-09-01

    Reduced graphene oxides (RGOs) have usually been obtained by hydrazine reduction, but hydrazine-related compounds are corrosive, highly flammable and very hazardous, and the obtained RGOs heavily aggregated. Here we investigated extensively the effect of temperature and pH value on the structure of RGOs in hydrothermal environments without any reducing agents. The attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra showed that reduction rate of GOs remarkably increased with the temperature from 100 to 180 °C and with pH value from 3 to 10. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) exhibited the structural transition of the RGOs. Energy-dispersive x-ray analysis (EDX) showed the reduction degree of the RGO samples quantitatively. The results demonstrate that the GOs can be reduced controllably by a hydrothermal reduction process at pH value of 10 at 140 °C, and the large-scale RGOs are cut into small nanosheets with size from several to a few tens of nanometers with increasing temperature and duration. This study provides a feasible approach to controllably reduce GO with different nanostructures such as porous structures and quantum dots for applications in optoelectronics and biomedicals.

  7. The metabolic N-oxidation of carcinogenic arylamines in relation to nitrogen charge density and oxidation potential

    SciTech Connect

    Kadlubar, F.F.; Fu, P.P.; Beland, F.A. ); Jung, Hyewook; Shaikh, A.U. )

    1990-07-01

    The N-oxidation of carcinogenic arylamines to form N-hydroxy arylamines has long been regarded as a necessary metabolic step for conversion to proximate carcinogenic derivatives. In contrast, arylamine ring-oxidation has been generally considered to be an important detoxification mechanism. Both enzymatic reactions are carried out in the liver and usually involve the cytochrome P-450 monooxygenases. studies on the metabolic oxidation of certain arylamines have indicated that the relative charge density on nitrogen versus ring-carbon atoms for a nitrenium/carbenium ion-enzyme intermediate correlates with the relative proportion of N-versus ring-hydroxylated products that are formed. Since greater positive charge on the arylamine nitrogen implies a greater charge localization during the transition state of the enzyme-substrate complex, the authors envisioned that higher oxidation potentials for arylamines, which might be expected to correlate inversely with the ease of total oxidation, would instead be predictive of the relative extent of N-oxidation. When the half-wave oxidation potentials (E{sub 1/2}'s) of the above-mentioned arylamines, along with those of 1-amino-6-nitropyrene and 1-amino-8-nitropyrene (which also undergo N-oxidation but are not amenable to simple Hueckel calculations), were experimentally determined by linear sweep voltammetry, an E{sub 1/2} of greater than + 0.60 V was found to be generally predictive of the ability of these arylamines to undergo metabolic N-oxidation. Thus, these methods may be applicable to other arylamines whose extent of N-oxidation and carcinogenic potential are unknown.

  8. Syntrophic Effects in a Subsurface Clostridial Consortium on Fe(III)-(Oxyhydr)oxide Reduction and Secondary Mineralization

    SciTech Connect

    Shah, Madhavi; Lin, Chu-Ching; Kukkadapu, Ravi K.; Engelhard, Mark H.; Zhao, Xiuhong; Wang, Yangping; Barkay, Tamar; Yee, Nathan

    2013-12-02

    In this study, we cultivated from subsurface sediments an anaerobic Clostridia 25 consortium that was composed of a fermentative Fe-reducer Clostridium species (designated as 26 strain FGH) and a novel sulfate-reducing bacterium belonging to the Clostridia family 27 Vellionellaceae (designated as strain RU4). In pure culture, Clostridium sp. strain FGH mediated 28 the reductive dissolution/transformation of iron oxides during growth on peptone. When 29 Clostridium sp. FGH was grown with strain RU4 on peptone, the rates of iron oxide reduction 30 were significantly higher. Iron reduction by the consortium was mediated by multiple 31 mechanisms, including biotic reduction by Clostridium sp. FGH and biotic/abiotic reactions 32 involving biogenic sulfide by strain RU4. The Clostridium sp. FGH produced hydrogen during 33 fermentation, and the presence of hydrogen inhibited growth and iron reduction activity. The 34 sulfate-reducing partner strain RU4 was stimulated by the presence of H2 gas and generated 35 reactive sulfide which promoted the chemical reduction of the iron oxides. Characterization of 36 Fe(II) mineral products showed the formation of magnetite during ferrihydrite reduction, and 37 the precipitation of iron sulfides during goethite and hematite reduction. The results suggest an 38 important pathway for iron reduction and secondary mineralization by fermentative sulfate-39 reducing microbial consortia is through syntrophy-driven biotic/abiotic reactions with biogenic 40 sulfide.

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

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtlu

    2003-11-30

    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. 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, the effect of promoters on the activity and selectivity of copper oxide/cerium oxide-based catalysts and the reaction mechanism for the SCR with methane was investigated. Unpromoted and promoted 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 the other metals (Rh, Li, K, Na, Zn, and Sn) for the supported copper oxide-ceria catalysts under study. The effectiveness of the promoter increased with the increase in Ce/Cu ratio. Among the catalysts tested, the Cu1Ce3 catalyst promoted with 1 weight % Mn was found to be the best catalyst for the SCR of NO with methane. This catalyst was subjected to long-term testing at the facilities of our industrial partner TDA Research. TDA report indicated that the performance of this catalyst did not deteriorate during 100 hours of operation and the activity and selectivity of the catalyst was not affected by the presence of SO{sub 2}. The conversions obtained by TDA were significantly lower than those obtained at Hampton University due to the transport limitations on the reaction rate in the TDA reactor, in which 1/8th inch pellets were used while the Hampton University reactor contained 250-425-{micro}m catalyst particles. The selected catalyst was also tested at the TDA facilities with high-sulfur heavy oil as the reducing agent. Depending on the heavy oil flow rate, up to 100% NO conversions were obtained. The temperature programmed desorption studies a strong interaction between manganese and cerium. Presence of manganese not only enhanced the reduction rate of NO by methane, but also significantly improved the N{sub 2} selectivity. To increase the activity of the Mn-promoted catalyst, the manganese content of the catalyst need to be optimized and different methods of catalyst preparation and different reactor types need to be investigated to lower the transport limitations in the reactor.

  10. Oxidative stress in kidney transplantation: causes, consequences, and potential treatment.

    E-print Network

    Nafar, Mohsen; Sahraei, Zahra; Salamzadeh, Jamshid; Samavat, Shiva; Vaziri, Nosartolah D

    2011-01-01

    antioxidant status in transplant recipients causing transplant recipients to be at higher risk of skin cancer.antioxidants. Besides adversely affecting the allograft, oxidative stress and its constant companion, inflammation, cause cardiovascular disease, cancer,

  11. Passivated iodine pentoxide oxidizer for potential biocidal nanoenergetic applications.

    PubMed

    Feng, Jingyu; Jian, Guoqiang; Liu, Qing; Zachariah, Michael R

    2013-09-25

    Iodine pentoxide (I2O5), also known as diiodine pentoxide, is a strong oxidizer which has been recently proposed as an iodine-rich oxidizer in nanoenergetic formulations, whose combustion products lead to molecular iodine as a biocidal agent. However, its highly hygroscopic nature hinders its performance as a strong oxidizer and an iodine releasing agent and prevents its implementation. In this work, we developed a gas phase assisted aerosol spray pyrolysis which enables creation of iron oxide passivated I2O5. Transmission electron microscopy elemental imaging as well as temperature-jump mass spectrometry confirmed the core shell nature of the material and the fact that I2O5 could be encapsulated in pure unhydrated form. Combustion performance finds an optimal coating thickness that enables combustion performance similar to a high performing CuO based thermite. PMID:23988006

  12. 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...

  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. (page number not for citation purposes) Prediction of reduction potentials from calculated

    E-print Network

    Gherman, Benjamin F.

    Page 1 of (page number not for citation purposes) 6 Prediction of reduction potentials from of (page number not for citation purposes) 6 Introduction The electroreductive cyclization (ERC) reaction Chemistry 2009, 5, No. 82. Page 2 of (page number not for citation purposes) 6 Figure 1: Training set of 19

  15. Submerged Liquid Plasma for the Synchronized Reduction and Functionalization of Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Senthilnathan, Jaganathan; Liu, Yung-Fang; Rao, Kodepelly Sanjeeva; Yoshimura, Masahiro

    2014-03-01

    Formation of reduced and functionalized graphene oxide (r-FGO) at ambient temperature and pressure is demonstrated by generating liquid plasma submerged in acetonitrile and graphene oxide solution. The partial restoration of conjugation (sp2 domain) and insertion of fluorophores such as nitrile and amine in r-FGO displays enhanced fluorescence property. Presence of nitrile and amine in r-FGO are confirmed by X-ray photoelectron spectroscopy and Fourier transforms infrared spectroscopy. Morphology and optical property of r-FGO are studied with transmission electron microscopy, scanning tunneling microscopy and Ultraviolet-visible spectroscopy measurements. The nitrile and amine present in r-FGO undergo a surface-controlled reversible redox reaction and sp2- enriched r-FGO acts as an electrical double layer, providing additional hybrid capacitance or pseudocapacitance. r-FGO shows high cyclic stability with a specific capacitance value of 349 F/g at the scan rate of 10 mV/s. Only marginal reduction of specific capacitance (<10% reduction) is observed at the end of 1000 cycles.

  16. Evaluation of Corona Reactors of Several Geometries for a Plasma Assisted Nitrogen Oxide Emission Reduction Device

    SciTech Connect

    Herling, Darrell R.; Smith, Monty R.; Hemingway, Mark D.; Goulette, David; Silvis, Thomas W.

    2000-08-09

    Proposed vehicle emissions regulations for the near future have prompted automotive manufactures and component suppliers to focus heavily on developing more efficient exhaust aftertreatment devices to lower emissions from spark and compression ignition engines. One of the primary pollutants from lean-burn engines, especially from diesels, are oxides of nitrogen (NOx). Current three-way catalytic converters will not have adequate performance to meet future emission reduction requirements. Therefore, there is a need for researchers and engineers to develop efficient exhaust aftertreatment devices that will reduce NOx emissions from lean-burn engines. These devices must have very high conversion of NOx gases, be unaffected by exhaust-gas impurity such as sulfur, and have minimal impact on vehicle operations and fuel economy. An effective technology for NOx control that is currently receiving a lot of attention is a non-thermal plasma system. This system is comprised of a two-stage corona generation device (plasma reactor) and reduction catalyst that reduces nitric oxide and nitrogen dioxide emissions to nitrogen.

  17. Photocatalytic carbon dioxide reduction by copper oxide nanocluster-grafted niobate nanosheets.

    PubMed

    Yin, Ge; Nishikawa, Masami; Nosaka, Yoshio; Srinivasan, Nagarajan; Atarashi, Daiki; Sakai, Etsuo; Miyauchi, Masahiro

    2015-02-24

    Amorphous copper oxide (Cu(II)) nanoclusters function as efficient electrocatalysts for the reduction of carbon dioxide (CO2) to carbon monoxide (CO). In addition to promoting electrocatalytic activity, Cu(II) nanoclusters act as efficient cocatalyts for CO2 photoreduction when grafted onto the surface of a semiconductor (light harvester), such as niobate (Nb3O8(-)) nanosheets. Here, the photocatalytic activity and reaction pathway of Cu(II)-grafted Nb3O8(-) nanosheets was investigated using electron spin resonance (ESR) analysis and isotope-labeled molecules (H2(18)O and (13)CO2). The results of the labeling experiments demonstrated that under UV irradiation, electrons are extracted from water to produce oxygen ((18)O2) and then reduce CO2 to produce (13)CO. ESR analysis confirmed that excited holes in the valence band of Nb3O8(-) nanosheets react with water, and that excited electrons in the conduction band of Nb3O8(-) nanosheets are injected into the Cu(II) nanoclusters through the interface and are involved in the reduction of CO2 into CO. The Cu(II) nanocluster-grafted Nb3O8(-) nanosheets are composed of nontoxic and abundant elements and can be facilely synthesized by a wet chemical method. The nanocluster grafting technique described here can be applied for the surface activation of various semiconductor light harvesters, such as metal oxide and/or metal chalcogenides, and is expected to aid in the development of efficient CO2 photoreduction systems. PMID:25629438

  18. Submerged Liquid Plasma for the Synchronized Reduction and Functionalization of Graphene Oxide

    PubMed Central

    Senthilnathan, Jaganathan; Liu, Yung-Fang; Rao, Kodepelly Sanjeeva; Yoshimura, Masahiro

    2014-01-01

    Formation of reduced and functionalized graphene oxide (r-FGO) at ambient temperature and pressure is demonstrated by generating liquid plasma submerged in acetonitrile and graphene oxide solution. The partial restoration of conjugation (sp2 domain) and insertion of fluorophores such as nitrile and amine in r-FGO displays enhanced fluorescence property. Presence of nitrile and amine in r-FGO are confirmed by X-ray photoelectron spectroscopy and Fourier transforms infrared spectroscopy. Morphology and optical property of r-FGO are studied with transmission electron microscopy, scanning tunneling microscopy and Ultraviolet–visible spectroscopy measurements. The nitrile and amine present in r-FGO undergo a surface-controlled reversible redox reaction and sp2- enriched r-FGO acts as an electrical double layer, providing additional hybrid capacitance or pseudocapacitance. r-FGO shows high cyclic stability with a specific capacitance value of 349?F/g at the scan rate of 10?mV/s. Only marginal reduction of specific capacitance (<10% reduction) is observed at the end of 1000 cycles. PMID:24637779

  19. Nitrite reduction by molybdoenzymes: a new class of nitric oxide-forming nitrite reductases.

    PubMed

    Maia, Luisa B; Moura, José J G

    2015-03-01

    Nitric oxide (NO) is a signalling molecule involved in several physiological processes, in both prokaryotes and eukaryotes, and nitrite is being recognised as an NO source particularly relevant to cell signalling and survival under challenging conditions. The "non-respiratory" nitrite reduction to NO is carried out by "non-dedicated" nitrite reductases, making use of metalloproteins present in cells to carry out other functions, such as several molybdoenzymes (a new class of nitric oxide-forming nitrite reductases). This minireview will highlight the physiological relevance of molybdenum-dependent nitrite-derived NO formation in mammalian, plant and bacterial signalling (and other) pathways. The mammalian xanthine oxidase/xanthine dehydrogenase, aldehyde oxidase, mitochondrial amidoxime-reducing component, plant nitrate reductase and bacterial aldehyde oxidoreductase and nitrate reductases will be considered. The nitrite reductase activity of each molybdoenzyme will be described and the review will be oriented to discuss the feasibility of the reactions from a (bio)chemical point of view. In addition, the molecular mechanism proposed for the molybdenum-dependent nitrite reduction will be discussed in detail. PMID:25589250

  20. Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

    PubMed Central

    Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

    2015-01-01

    The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e?, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

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

    SciTech Connect

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

    2011-12-13

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

  2. A predictive mechanism for mercury oxidation on selective catalytic reduction catalysts under coal-derived flue gas

    SciTech Connect

    Stephen Niksa; Naoki Fujiwara

    2005-12-15

    This paper introduces a predictive mechanism for elemental mercury (Hg{sup 0}) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH{sub 3})/nitric oxide (NO) ratio and concentrations of Hg{sup 0} and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg{sup 0} oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH{sub 3} and that Hg{sup 0} contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg{sup 0} oxidation by NH{sub 3}, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH{sub 3} adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg{sup 0} oxidation. But once NH{sub 3} has been consumed, the Hg{sup 0} oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region factors that enhance surface chlorination, promote Hg{sup 0} oxidation. This mechanism accurately interprets the reported tendencies for greater extents of Hg{sup 0} oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg{sup 0} oxidation for hotter temperatures on plate monoliths. The mechanism reproduces the reported extents of Hg{sup 0} oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions. 28 refs., 5 figs., 3 tabs.

  3. The Preparation and Reduction Behavior of Charcoal Composite Iron Oxide Pellets

    NASA Astrophysics Data System (ADS)

    Konishi, Hirokazu; Usui, Tateo; Harada, Takeshi

    In the energy conversion, biomass has novel advantage, i.e., no CO2 emission, because of carbon neutral. Charcoal composite iron oxide pellets were proposed to decrease CO2 emission for the ironmaking. These pellets were promising to decrease the initial temperature for reduction reaction of carbon composite iron ore agglomerate under a rising temperature condition, such as in a blast furnace shaft. In order to obtain charcoal, Japanese cedar and cypress were carbonized from room temperature to maximum carbonization temperature (TC, max = 1273 K) at a heating rate of 200 K/h, and kept at TC, max until arrival time of 6 h. Reducing gases of CO and CH4 started releasing from relatively low temperature (500 K). In the total gas volume of carbonization, H2 gas of Japanese cedar was more than that of Japanese cypress. These woods have more CO gas volume than Newcastle blend coal has. The obtained charcoal was mixed with reagent grade hematite in the mass ratio of one to four. Then, a small amount of Bentonite was added to the mixture as a binder, and the charcoal composite iron oxide pellets were prepared and reduced at 1273, 1373 and 1473 K in nitrogen gas atmosphere. It was conirmed by the generated gas analysis during reduction reaction that charcoal composite iron oxide pellets had higher reducibility than char composite pellets using Newcastle blend coal. From the XRD analysis of the reduced pellets, it was found that the original Fe2O3 was almost reduced to Fe for 60 min at 1273 K, 20 min at 1373 K and 5~15 min at 1473 K.

  4. Apparatus and process for the electrolytic reduction of uranium and plutonium oxides

    DOEpatents

    Poa, David S. (Naperville, IL); Burris, Leslie (Naperville, IL); Steunenberg, Robert K. (Naperville, IL); Tomczuk, Zygmunt (Orland Park, IL)

    1991-01-01

    An apparatus and process for reducing uranium and/or plutonium oxides to produce a solid, high-purity metal. The apparatus is an electrolyte cell consisting of a first container, and a smaller second container within the first container. An electrolyte fills both containers, the level of the electrolyte in the first container being above the top of the second container so that the electrolyte can be circulated between the containers. The anode is positioned in the first container while the cathode is located in the second container. Means are provided for passing an inert gas into the electrolyte near the lower end of the anode to sparge the electrolyte and to remove gases which form on the anode during the reduction operation. Means are also provided for mixing and stirring the electrolyte in the first container to solubilize the metal oxide in the electrolyte and to transport the electrolyte containing dissolved oxide into contact with the cathode in the second container. The cell is operated at a temperature below the melting temperature of the metal product so that the metal forms as a solid on the cathode.

  5. Reduction of Tc(VII) by Fe(II) Sorbed on Al (hydr)oxides

    SciTech Connect

    Peretyazhko, Tetyana; Zachara, John M.; Heald, Steve M.; Kukkadapu, Ravi K.; Liu, Chongxuan; Plymale, Andrew E.; Resch, Charles T.

    2008-08-01

    Technetium speciation, solubility and sorption behavior is strongly dependent on its valence state. Under oxic conditions, Tc exists as the soluble, weakly-sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2·xH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides [diaspore (?-AlOOH) and corundum (?-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (Mössbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11d (diaspore suspension) and 4d (corundum suspension). Mössbauer measurements revealed that the Fe(II) signal became less intense with Tc(VII) reduction, and was accompanied by increase in Fe(III) doublet and magnetically-ordered Fe(III) sextet signals, with latter parameters close to those for hematite. Formation of magnetically ordered Fe(III) did not depend on the oxidant nature, as both Tc(VII) or O2 lead to the formation of a virtually identical hematite-like phase. The Fe(II) doublet displayed no differences in Mössbauer parameters before and after Tc(VII) reduction, likely due to Fe(II) adsorption to similar sites and no Fe(II) sorption to or precipitation within solid phases formed. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2?xH2O. The formation of precursor polymeric TcnOy (4n-2y)+ chains prior to TcO2?xH2O precipitation might explain the formation of the separate TcO2-like phase on corundum without coprecipitated Fe.

  6. Thermal, solution and reductive decomposition of Cu-Al layered double hydroxides into oxide products

    SciTech Connect

    Britto, Sylvia; Vishnu Kamath, P.

    2009-05-15

    Cu-Al layered double hydroxides (LDHs) with [Cu]/[Al] ratio 2 adopt a structure with monoclinic symmetry while that with the ratio 0.25 adopt a structure with orthorhombic symmetry. The poor thermodynamic stability of the Cu-Al LDHs is due in part to the low enthalpies of formation of Cu(OH){sub 2} and CuCO{sub 3} and in part to the higher solubility of the LDH. Consequently, the Cu-Al LDH can be decomposed thermally (150 deg. C), hydrothermally (150 deg. C) and reductively (ascorbic acid, ambient temperature) to yield a variety of oxide products. Thermal decomposition at low (400 deg. C) temperature yields an X-ray amorphous residue, which reconstructs back to the LDH on soaking in water or standing in the ambient. Solution decomposition under hydrothermal conditions yields tenorite at 150 deg. C itself. Reductive decomposition yields a composite of Cu{sub 2}O and Al(OH){sub 3}, which on alkali-leaching of the latter, leads to the formation of fine particles of Cu{sub 2}O (<1 {mu}m). - Graphical abstract: SEM image of (a) the Cu{sub 2}O-Al(OH){sub 3} composite obtained on reductive decomposition of CuAl{sub 4}-LDH and (b) Cu{sub 2}O obtained on leaching of Al(OH){sub 3} from (a).

  7. Oxidant production from source-oriented particulate matter - Part 1: Oxidative potential using the dithiothreitol (DTT) assay

    NASA Astrophysics Data System (ADS)

    Charrier, J. G.; Richards-Henderson, N. K.; Bein, K. J.; McFall, A. S.; Wexler, A. S.; Anastasio, C.

    2015-03-01

    Recent epidemiological evidence supports the hypothesis that health effects from inhalation of ambient particulate matter (PM) are governed by more than just the mass of PM inhaled. Both specific chemical components and sources have been identified as important contributors to mortality and hospital admissions, even when these end points are unrelated to PM mass. Sources may cause adverse health effects via their ability to produce reactive oxygen species in the body, possibly due to the transition metal content of the PM. Our goal is to quantify the oxidative potential of ambient particle sources collected during two seasons in Fresno, CA, using the dithiothreitol (DTT) assay. We collected PM from different sources or source combinations into different ChemVol (CV) samplers in real time using a novel source-oriented sampling technique based on single-particle mass spectrometry. We segregated the particles from each source-oriented mixture into two size fractions - ultrafine Dp ? 0.17 ?m) and submicron fine (0.17 ?m ? Dp ? 1.0 ?m) - and measured metals and the rate of DTT loss in each PM extract. We find that the mass-normalized oxidative potential of different sources varies by up to a factor of 8 and that submicron fine PM typically has a larger mass-normalized oxidative potential than ultrafine PM from the same source. Vehicular emissions, regional source mix, commute hours, daytime mixed layer, and nighttime inversion sources exhibit the highest mass-normalized oxidative potential. When we apportion DTT activity for total PM sampled to specific chemical compounds, soluble copper accounts for roughly 50% of total air-volume-normalized oxidative potential, soluble manganese accounts for 20%, and other unknown species, likely including quinones and other organics, account for 30%. During nighttime, soluble copper and manganese largely explain the oxidative potential of PM, while daytime has a larger contribution from unknown (likely organic) species.

  8. Environmental Asthma Reduction Potential Estimates for Selected Mitigation Actions in Finland Using a Life Table Approach

    PubMed Central

    Rumrich, Isabell Katharina; Hänninen, Otto

    2015-01-01

    Aims: To quantify the reduction potential of asthma in Finland achievable by adjusting exposures to selected environmental factors. Methods: A life table model for the Finnish population for 1986–2040 was developed and Years Lived with Disability caused by asthma and attributable to the following selected exposures were estimated: tobacco smoke (smoking and second hand tobacco smoke), ambient fine particles, indoor dampness and mould, and pets. Results: At baseline (2011) about 25% of the total asthma burden was attributable to the selected exposures. Banning tobacco was the most efficient mitigation action, leading to 6% reduction of the asthma burden. A 50% reduction in exposure to dampness and mould as well as a doubling in exposure to pets lead each to a 2% reduction. Ban of urban small scale wood combustion, chosen as a mitigation action to reduce exposure to fine particles, leads to a reduction of less than 1% of the total asthma burden. Combination of the most efficient mitigation actions reduces the total asthma burden by 10%. A more feasible combination of mitigation actions leads to 6% reduction of the asthma burden. Conclusions: The adjustment of environmental exposures can reduce the asthma burden in Finland by up to 10%. PMID:26067987

  9. An Inner Membrane Cytochrome Required Only for Reduction of High Redox Potential Extracellular Electron Acceptors

    PubMed Central

    Levar, Caleb E.; Chan, Chi Ho; Mehta-Kolte, Misha G.

    2014-01-01

    ABSTRACT Dissimilatory metal-reducing bacteria, such as Geobacter sulfurreducens, transfer electrons beyond their outer membranes to Fe(III) and Mn(IV) oxides, heavy metals, and electrodes in electrochemical devices. In the environment, metal acceptors exist in multiple chelated and insoluble forms that span a range of redox potentials and offer different amounts of available energy. Despite this, metal-reducing bacteria have not been shown to alter their electron transfer strategies to take advantage of these energy differences. Disruption of imcH, encoding an inner membrane c-type cytochrome, eliminated the ability of G. sulfurreducens to reduce Fe(III) citrate, Fe(III)-EDTA, and insoluble Mn(IV) oxides, electron acceptors with potentials greater than 0.1 V versus the standard hydrogen electrode (SHE), but the imcH mutant retained the ability to reduce Fe(III) oxides with potentials of ??0.1 V versus SHE. The imcH mutant failed to grow on electrodes poised at +0.24 V versus SHE, but switching electrodes to ?0.1 V versus SHE triggered exponential growth. At potentials of ??0.1 V versus SHE, both the wild type and the imcH mutant doubled 60% slower than at higher potentials. Electrodes poised even 100 mV higher (0.0 V versus SHE) could not trigger imcH mutant growth. These results demonstrate that G. sulfurreducens possesses multiple respiratory pathways, that some of these pathways are in operation only after exposure to low redox potentials, and that electron flow can be coupled to generation of different amounts of energy for growth. The redox potentials that trigger these behaviors mirror those of metal acceptors common in subsurface environments where Geobacter is found. PMID:25425235

  10. An inner membrane cytochrome required only for reduction of high redox potential extracellular electron acceptors

    SciTech Connect

    Levar, Caleb E.; Chan, Chi Ho; Mehta-Kolte, Misha G.; Bond, Daniel R.

    2014-10-28

    Dissimilatory metal-reducing bacteria, such as Geobacter sulfurreducens, transfer electrons beyond their outer membranes to Fe(III) and Mn(IV) oxides, heavy metals, and electrodes in electrochemical devices. In the environment, metal acceptors exist in multiple chelated and insoluble forms that span a range of redox potentials and offer different amounts of available energy. Despite this, metal-reducing bacteria have not been shown to alter their electron transfer strategies to take advantage of these energy differences. Disruption of imcH, encoding an inner membrane c-type cytochrome, eliminated the ability of G. sulfurreducens to reduce Fe(III) citrate, Fe(III)-EDTA, and insoluble Mn(IV) oxides, electron acceptors with potentials greater than 0.1 V versus the standard hydrogen electrode (SHE), but the imcH mutant retained the ability to reduce Fe(III) oxides with potentials of ?–0.1 V versus SHE. The imcH mutant failed to grow on electrodes poised at +0.24 V versus SHE, but switching electrodes to –0.1 V versus SHE triggered exponential growth. At potentials of ?–0.1 V versus SHE, both the wild type and the imcH mutant doubled 60% slower than at higher potentials. Electrodes poised even 100 mV higher (0.0 V versus SHE) could not trigger imcH mutant growth. These results demonstrate that G. sulfurreducens possesses multiple respiratory pathways, that some of these pathways are in operation only after exposure to low redox potentials, and that electron flow can be coupled to generation of different amounts of energy for growth. Redox potentials that trigger these behaviors mirror those of metal acceptors common in subsurface environments where Geobacter is found.

  11. Metabolic potential of fatty acid oxidation and anaerobic respiration by abundant members of Thaumarchaeota and Thermoplasmata in deep anoxic peat.

    PubMed

    Lin, Xueju; Handley, Kim M; Gilbert, Jack A; Kostka, Joel E

    2015-12-01

    To probe the metabolic potential of abundant Archaea in boreal peats, we reconstructed two near-complete archaeal genomes, affiliated with Thaumarchaeota group 1.1c (bin Fn1, 8% abundance), which was a genomically unrepresented group, and Thermoplasmata (bin Bg1, 26% abundance), from metagenomic data acquired from deep anoxic peat layers. Each of the near-complete genomes encodes the potential to degrade long-chain fatty acids (LCFA) via ?-oxidation. Fn1 has the potential to oxidize LCFA either by syntrophic interaction with methanogens or by coupling oxidation with anaerobic respiration using fumarate as a terminal electron acceptor (TEA). Fn1 is the first Thaumarchaeota genome without an identifiable carbon fixation pathway, indicating that this mesophilic phylum encompasses more diverse metabolisms than previously thought. Furthermore, we report genetic evidence suggestive of sulfite and/or organosulfonate reduction by Thermoplasmata Bg1. In deep peat, inorganic TEAs are often depleted to extremely low levels, yet the anaerobic respiration predicted for two abundant archaeal members suggests organic electron acceptors such as fumarate and organosulfonate (enriched in humic substances) may be important for respiration and C mineralization in peatlands. PMID:26000553

  12. Theoretical Determination of One-Electron Oxidation Potentials for Nucleic Acid Bases

    E-print Network

    Schlegel, H. Bernhard

    Theoretical Determination of One-Electron Oxidation Potentials for Nucleic Acid Bases Brian T potentials for N-methyl substituted nucleic acid bases guanine, adenine, cytosine, thymine, uracil, xanthine of redox potentials for the standard nucleic acids guanine, adenine, cytosine, thymine, and uracil

  13. SOIL ORGANIC MATTER OXIDATION POTENTIAL WITH FLUCTUATING WATER TABLE UNDER SUGARCANE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Histosols in the Everglades Agricultural Area are subsiding primarily from aerobic microbial oxidation. Flooding reduces soil subsidence. An experiment was set up in lysimeters with sugarcane growing in muck soil to determine oxidation potential under varying water-table levels after flood. Treatmen...

  14. THE OXIDATION OF ORGANIC COMPOUNDS IN THE TROPOSPHERE AND THEIR GLOBAL WARMING POTENTIALS

    E-print Network

    Stevenson, David

    pulses of 10 organic compounds were followed in a global 3-D Lagrangian chemistry-transport modelTHE OXIDATION OF ORGANIC COMPOUNDS IN THE TROPOSPHERE AND THEIR GLOBAL WARMING POTENTIALS W. J by hydroxyl radicals is the main removal process for organic compounds in the troposphere. This oxidation acts

  15. POTENTIALLY GOOD REDUCTION OF BARSOTTI-TATE Abstract. Let R be a complete discrete valuation ring of mixed character-

    E-print Network

    Liu, Tong

    POTENTIALLY GOOD REDUCTION OF BARSOTTI-TATE GROUPS TONG LIU Abstract. Let R be a complete discrete. Suppose G is a Barsotti-Tate group (p-divisible group) defined over K which acquires good reduction over ramification index e(K /Qp) and the height of G such that G has good reduction over K if and only if G[pc] can

  16. Rationally Tuning the Reduction Potential of a Single Cupredoxin Beyond the Natural Range

    SciTech Connect

    Marshall, N.; Garner, D; Wilson, T; Gao, Y; Robinson, H; Nilges, M; Lu, Y

    2009-01-01

    Redox processes are at the heart of numerous functions in chemistry and biology, from long-range electron transfer in photosynthesis and respiration to catalysis in industrial and fuel cell research. These functions are accomplished in nature by only a limited number of redox-active agents. A long-standing issue in these fields is how redox potentials are fine-tuned over a broad range with little change to the redox-active site or electron-transfer properties. Resolving this issue will not only advance our fundamental understanding of the roles of long-range, non-covalent interactions in redox processes, but also allow for design of redox-active proteins having tailor-made redox potentials for applications such as artificial photosynthetic centres or fuel cell catalysts for energy conversion. Here we show that two important secondary coordination sphere interactions, hydrophobicity and hydrogen-bonding, are capable of tuning the reduction potential of the cupredoxin azurin over a 700 mV range, surpassing the highest and lowest reduction potentials reported for any mononuclear cupredoxin, without perturbing the metal binding site beyond what is typical for the cupredoxin family of proteins. We also demonstrate that the effects of individual structural features are additive and that redox potential tuning of azurin is now predictable across the full range of cupredoxin potentials.

  17. An inner membrane cytochrome required only for reduction of high redox potential extracellular electron acceptors

    DOE PAGESBeta

    Levar, Caleb E.; Chan, Chi Ho; Mehta-Kolte, Misha G.; Bond, Daniel R.

    2014-10-28

    Dissimilatory metal-reducing bacteria, such as Geobacter sulfurreducens, transfer electrons beyond their outer membranes to Fe(III) and Mn(IV) oxides, heavy metals, and electrodes in electrochemical devices. In the environment, metal acceptors exist in multiple chelated and insoluble forms that span a range of redox potentials and offer different amounts of available energy. Despite this, metal-reducing bacteria have not been shown to alter their electron transfer strategies to take advantage of these energy differences. Disruption of imcH, encoding an inner membrane c-type cytochrome, eliminated the ability of G. sulfurreducens to reduce Fe(III) citrate, Fe(III)-EDTA, and insoluble Mn(IV) oxides, electron acceptors with potentialsmore »greater than 0.1 V versus the standard hydrogen electrode (SHE), but the imcH mutant retained the ability to reduce Fe(III) oxides with potentials of ?–0.1 V versus SHE. The imcH mutant failed to grow on electrodes poised at +0.24 V versus SHE, but switching electrodes to –0.1 V versus SHE triggered exponential growth. At potentials of ?–0.1 V versus SHE, both the wild type and the imcH mutant doubled 60% slower than at higher potentials. Electrodes poised even 100 mV higher (0.0 V versus SHE) could not trigger imcH mutant growth. These results demonstrate that G. sulfurreducens possesses multiple respiratory pathways, that some of these pathways are in operation only after exposure to low redox potentials, and that electron flow can be coupled to generation of different amounts of energy for growth. Redox potentials that trigger these behaviors mirror those of metal acceptors common in subsurface environments where Geobacter is found.« less

  18. Indirect electrochemical Cr(III) oxidation in KOH solutions at an Au electrode: the role of oxygen reduction reaction.

    PubMed

    Jin, Wei; Moats, Michael S; Zheng, Shili; Du, Hao; Zhang, Yi; Miller, Jan D

    2012-06-28

    The indirect electro-oxidation of Cr(III) by in situ generated superoxide at a gold electrode has been investigated in KOH solutions using cyclic voltammetry and UV-vis spectroscopy. It is observed that the indirect Cr(III) oxidation behavior is substantially affected by the media pH and there is a pH-modulated oxygen reduction reaction (ORR) process to generate reactive oxygen species which promotes Cr(III) oxidation. The ORR in KOH solutions is attributed to a quasi-reversible diffusion-controlled reaction. In dilute KOH solution (0.2 M), 4e reduction occurs and no reactive oxygen species are generated for the indirect Cr(III) oxidation. Moreover, Cr(III) oxidation is inhibited due to competition for the electrode active sites. As the alkaline concentration increases (3.0 M), the protonation of superoxide is greatly suppressed, and thus, 1e ORR to generate superoxide is observed. This change in mechanism facilitates the indirect Cr(III) oxidation through the superoxide as a mediator to oxidize Cr(III) to Cr(IV), which is the rate-determining step of Cr(III) oxidation to Cr(VI). PMID:22668248

  19. Treatment of activated carbon to enhance catalytic activity for reduction of nitric oxide with ammonia

    SciTech Connect

    Ku, B.J.; Rhee, H.K. . Dept. of Chemical Engineering); Lee, J.K.; Park, D. )

    1994-11-01

    Catalytic activity of activated carbon treated with various techniques was examined in a fixed bed reactor for the reduction of nitric oxide with ammonia at 150 C. Activated carbon derived from coconut shell impregnated with an aqueous solution of ammonium sulfate, further treated with sulfuric acid, dried at 120 C, and then heated in an inert gas stream at 400 C, showed the highest catalytic activity within the range of experimental conditions. The enhancement of catalytic activity of modified activated carbon could be attributed to the increase in the amount of oxygen function groups which increased the adsorption site for ammonia. Catalytic activity of activated carbons depended on the surface area and the oxygen content as well.

  20. Transient storage of photochemically produced oxidative and reductive equivalents in soluble redox polymers

    SciTech Connect

    Margerum, L.D.; Murray, R.W.; Meyer, T.J.

    1986-02-27

    Optical excitation and electron-transfer quenching of the metal to ligand charge-transfer (MLCT) excited state(s) of ((5-NH/sub 2/-phen)Ru(bpy)/sub 2/)/sup 2 +/ occur in solutions containing polystyrene polymers in which either pendant paraquat (PQ/sup 2 +/) or phenothiazine (PTZ) sites are attached. The quenching and subsequent electron-transfer steps lead to the appearance of -PQ/sup +/ and -PTZ/sup +/ on separate polymers. Since electron transfer between -PQ/sup +/ and -PTZ/sup +/ sites on separate polymers is slow, the lifetime of the photochemically produced oxidative and reductive equivalents is enhanced by approx.10/sup 3/ compared to related monomeric quenchers under similar conditions. 7 references, 1 figure.

  1. Combined Quantum Chemistry and Photoelectron Spectroscopy Study of the Electronic Structure and Reduction Potentials of Rubredoxin Redox Site Analogues

    SciTech Connect

    Niu, Shuqiang; Wang, Xue B.; Nichols, J. A.; Wang, Lai S.; Ichiye, Toshiko

    2003-04-24

    Iron-sulfur proteins are an important class of electron carriers in a wide variety of biological reactions. Determining the intrinsic contribution of the metal site to the redox potential is crucial in understanding how the protein environment influences the overall redox properties of the Fe-S proteins. Here we combine density functional theory and coupled cluster methods with photodetachment spectroscopy to study the electronic structures and gas-phase redox potentials of the [Fe(SCH3)(4)](2-/-/0) and [Fe(SCH3)(3)](-/0) analogues of the rubredoxin redox site. The calculations show that oxidations of [Fe(SCH3)(4)](2-) and [Fe(SCH3)(4)](-) involve mainly the Fe 3d and S 3p orbitals, respectively. The calculated adiabatic and vertical detachment energies are in good agreement with the experiment for [Fe(SCH3)(3)](-) and [Fe(SCH3)(4)](-). The current results further confirm the "inverted level scheme" for the high-spin [1Fe] systems. The redox couple, [Fe(SCH3)(4)](- /2), which is the one found in rubredoxin, but cannot be accessed experimentally in the gas phase, was investigated using a thermodynamic cycle that relates it to the [Fe(SCH3)(3)](-/0) couple and the ligand association reaction, [Fe(SCH3)(3)](0/-) + SCH3- --> [Fe(SCH3)(4)](-/2-). The calculated reduction energy of [Fe(SCH3)(4)](-) (1.7 eV) compares well with the value (1.6 eV) estimated from the calculated bond energies and the experimental detachment energy of [Fe(SCH3)(3)](-). Thus, this thermodynamic cycle method can be used to estimate metal-ligand bonding energies and determine intrinsic reduction potentials from photodetachment experiments when the reduced forms are not stable in the gas phase.

  2. Using LiST to model potential reduction in under-five mortality in Burkina Faso

    PubMed Central

    2013-01-01

    Background Under-five mortality remains high in Burkina Faso with significant reductions required to meet Millennium Development Goal 4. The Acceleration for Maternal, Newborn, and Child Health is being implemented to reduce child mortality in the North and Center North regions of Burkina Faso. Methods The Lives Saved Tool was used to determine the percent reduction in child mortality that can be achieved given baseline levels of coverage for interventions targeted by the Acceleration. Data were obtained from the Demographic and Health Survey 2003, the Multiple Indicator Cluster Survey 2006, and the baseline survey for the program from 2010. In addition to the scale up, scenarios were generated to examine the outcome if secular trends in intervention coverage change persisted and if intervention coverage levels remained constant. Results Scaling up all interventions to their target coverage level showed a potential reduction in under-five mortality of 22 percent, with district specific reductions in mortality ranging from 14 to 25 percent. The percent reduction in under-five mortality that might be attributable to the program was 16 percent and varied between 14 and 19 percent by district. Treatment of diarrhea with ORS and malaria with ACTs accounted for the majority of the reduction in mortality. Conclusions These findings suggest that significant reductions in under-five mortality may be achieved through the scale-up of the Acceleration. The Ministry of Health and its partners in Burkina Faso should continue their efforts to scale up these proven interventions to achieve and even exceed target levels for coverage. PMID:24564341

  3. Anodic Oxidation of m-terphenyl thio-, seleno-and telluroethers: Lowered oxidation potentials due to chalcogen.•••? interaction

    E-print Network

    Wilson, George S.; Ammam, Malika; Zakai, Uzma I.; Glass, Richard S.

    2010-02-01

    -Phase Electron Spectroscopy, The University of Arizona. REFERENCES AND NOTES 1. (a) R. S. Glass. In Sulfur-Centered Reactive Intermediates in Chemistry and Biology, C. Chatgilialoglu, K.-D. Asmus (Eds.), NATO ASI series 197, pp. 213–226, Plenum Press, New York... irreversible oxidations E°', the formal potential, and k°, the heterogeneous electron-transfer rate constant, largely determine the peak potential Ep at constant scan rate [10]. However, for a related series of sulfides, ionization energy dif- ferences follow...

  4. Chlorhexidine markedly potentiates the oxidants scavenging abilities of Candida albicans.

    PubMed

    Ginsburg, I; Koren, E; Feuerstein, O; Zogakis, I P; Shalish, M; Gorelik, S

    2015-10-01

    The oxidant scavenging ability (OSA) of catalase-rich Candida albicans is markedly enhanced by chlorhexidine digluconate (CHX), polymyxin B, the bile salt ursodeoxycholate and by lysophosphatidylcholine, which all act as detergents facilitating the penetration of oxidants and their intracellular decomposition. Quantifications of the OSA of Candida albicans were measured by a highly sensitive luminol-dependent chemiluminescence assay and by the Thurman's assay, to quantify hydrogen peroxide (H2O2). The OSA enhancing activity by CHX depends to some extent on the media on which candida grew. The OSA of candida treated by CHX was modulated by whole human saliva, red blood cells, lysozyme, cationic peptides and by polyphenols. Concentrations of CHX, which killed over 95 % of Candida albicans cells, did not affect the cells' abilities to scavenge reactive oxygen species (ROS). The OSA of Candida cells treated by CHX is highly refractory to H2O2 (50 mM) but is strongly inhibited by hypochlorous acid, lecithin, trypan blue and by heparin. We speculate that similarly to catalase-rich red blood cells, Candida albicans and additional catalase-rich microbiota may also have the ability to scavenge oxidants and thus can protect catalase-negative anaerobes and facultative anaerobes cariogenic streptococci against peroxide and thus secure their survival in the oral cavity. PMID:26223507

  5. Potential reduction of en route noise from an advanced turboprop aircraft

    NASA Technical Reports Server (NTRS)

    Dittmar, James H.

    1990-01-01

    When the en route noise of a representative aircraft powered by an eight-blade SR-7 propeller was previously calculated, the noise level was cited as a possible concern associated with the acceptance of advanced turboprop aircraft. Some potential methods for reducing the en route noise were then investigated and are reported. Source noise reductions from increasing the blade number and from operating at higher rotative speed to reach a local minimum noise point were investigated. Greater atmospheric attenuations for higher blade passing frequencies were also indicated. Potential en route noise reductions from these methods were calculated as 9.5 dB (6.5 dB(A)) for a 10-blade redesigned propeller and 15.5 dB (11 dB(A)) for a 12-blade redesigned propeller.

  6. On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

    NASA Astrophysics Data System (ADS)

    Pusede, S. E.; Duffey, K. C.; Shusterman, A. A.; Saleh, A.; Laughner, J. L.; Wooldridge, P. J.; Zhang, Q.; Parworth, C. L.; Kim, H.; Capps, S. L.; Valin, L. C.; Cappa, C. D.; Fried, A.; Walega, J.; Nowak, J. B.; Hoff, R. M.; Berkoff, T. A.; Beyersdorf, A. J.; Olson, J.; Crawford, J. H.; Cohen, R. C.

    2015-10-01

    Nitrogen oxides (NOx) have fallen steadily across the US over the last fifteen years. At the same time, due to patterns diesel truck activities, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations, they will also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

  7. Kidney-Specific Reduction of Oxidative Phosphorylation Genes Derived from Spontaneously Hypertensive Rat

    PubMed Central

    Collett, Jason A.; Paulose, Jiffin K.; Cassone, Vincent M.; Osborn, Jeffrey L.

    2015-01-01

    Mitochondrial (Mt) dysfunction contributes to the pathophysiology of renal function and promotes cardiovascular disease such as hypertension. We hypothesize that renal Mt-genes derived from female spontaneously hypertensive rats (SHR) that exhibit hypertension have reduced expression specific to kidney cortex. After breeding a female Okamoto-Aoki SHR (SAP = 188mmHg) with Brown Norway (BN) males (SAP = 100 and 104 mmHg), hypertensive female progeny were backcrossed with founder BN for 5 consecutive generations in order to maintain the SHR mitochondrial genome in offspring that contain over increasing BN nuclear genome. Mt-protein coding genes (13 total) and nuclear transcription factors mediating Mt-gene transcription were evaluated in kidney, heart and liver of normotensive (NT: n = 20) vs. hypertensive (HT: n = 20) BN/SHR-mtSHR using quantitative real-time PCR. Kidney cortex, but not liver or heart Mt-gene expression was decreased ~2–5 fold in 12 of 13 protein encoding genes of HT BN/SHR-mtSHR. Kidney cortex but not liver mRNA expression of the nuclear transcription factors Tfam, NRF1, NRF2 and Pgc1? were also decreased in HT BN/SHR-mtSHR. Kidney cortical tissue of HT BN/SHR-mtSHR exhibited lower cytochrome oxidase histochemical staining, indicating a reduction in renal oxidative phosphorylation but not in liver or heart. These results support the hypothesis that renal cortex of rats with SHR mitochondrial genome has specifically altered renal expression of genes encoding mitochondrial proteins. This kidney-specific coordinated reduction of mitochondrial and nuclear oxidative metabolism genes may be associated with heritable hypertension in SHR. PMID:26308211

  8. OXIDATIVE INACTIVATION OF THE PROTEASOME IN RPE: A POTENTIAL LINK BETWEEN OXIDATIVE STRESS AND UPREGULATION OF IL-8

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oxidative stress and inflammation are implicated in the pathogenesis of several age-related diseases. Stress-induced overproduction of inflammatory cytokines, such as interleukin-8 (IL-8), is one of the early events of inflammation. The objective of this study was to determine potential links betwee...

  9. The noise reduction potential of dual-stream coaxial rectangular improperly expanded jet flows

    NASA Technical Reports Server (NTRS)

    Dosanjh, Darshan; Spina, Eric F.

    1995-01-01

    The research performed began during Spring 1991 as a project to assess the noise reduction potential of rectangular coaxial nozzle configurations for improperly expanded jets. The research plan consisted of: (1) design of coaxial rectangular nozzle configuration by Syracuse graduate research assistant; (2) construction of nozzles by NASA Langley machinists; and (3) acquisition of preliminary acoustic and optical data for a variety of inner and outer jet pressure ratios.

  10. Factors that determine the unusually low reduction potential of cytochrome c550 in cyanobacterial photosystem II.

    PubMed

    Vrettos, J S; Reifler, M J; Kievit, O; Lakshmi, K V; de Paula, J C; Brudvig, G W

    2001-09-01

    A new purification protocol for cytochrome c550 (cyt c550) from His-tagged SYnechocYstis PCC 6803 photosystem II (PSII) was developed which allows the protein to be isolated in high yield and purity. Electron paramagnetic resonance spectroscopy of cyt c550, both free in solution and in intact PSII preparations, yields identical spectra with g values at 1.50, 2.23, and 2.87, which are characteristic for a ferric low-spin bis-histidine coordinated heme. The resonance Raman spectrum of the isolated protein exhibits features characteristic of bis-histidine axial ligation of the iron and a slight ruffling of the heme macrocycle. Together, these results indicate that the heme structure is not very different from most c-type cytochromes, and thus the structure of the heme does not account for its unusually low reduction potential. A direct electrochemical measurement of the reduction potential was performed using square wave voltammetry on a pyrolytic graphite edge electrode, yielding E1.2=-108 mV (vs. NHE) with a peak separation of 5 mV. This value is 150 mV more positive than that previously measured by redox titrations. Because the behavior of the protein in the electrochemistry experiments is indicative of adsorption to the electrode surface, we surmise that binding of the protein to the electrode excludes solvent water from the heme-binding site. We conclude that the degree of solvent exposure makes a significant contribution to the heme reduction potential. Similarly, the binding of cyt c550 to PSII may also reduce the solvent exposure of the heme, and so the direct electrochemical value of the reduction potential may be relevant to the protein in its native state. PMID:11681704

  11. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (?10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the ?18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a ?18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy-rich ceria during re-oxidation at room temperature. The quantified oxygen isotope fractionation factors are consistent with the direct involvement of O2 in the rate limiting step for ceria reoxidation in air at room temperature. While additional parameters may reduce some of the uncertainties in our approach, this study demonstrates that isotope effects can be an encouraging tool for studying oxygen transport kinetics in ceria and other oxides. In addition, our finding warns of the special cares and limits in using ceria as an exchange medium for laboratory triple oxygen isotope analysis of CO2 or other oxygen-bearing gases.

  12. Oxidant production from source-oriented particulate matter - Part 1: Oxidative potential using the dithiothreitol (DTT) assay

    NASA Astrophysics Data System (ADS)

    Charrier, J. G.; Richards-Henderson, N. K.; Bein, K. J.; McFall, A. S.; Wexler, A. S.; Anastasio, C.

    2014-09-01

    Recent epidemiological evidence supports the hypothesis that health effects from inhalation of ambient particulate matter (PM) are governed by more than just the mass of PM inhaled. Both specific chemical components and sources have been identified as important contributors to mortality and hospital admissions, even when these endpoints are unrelated to PM mass. Sources may cause adverse health effects via their ability to produce reactive oxygen species, possibly due to the transition metal content of the PM. Our goal is to quantify the oxidative potential of ambient particle sources collected during two seasons in Fresno, CA using the dithiothreitol (DTT) assay. We collected PM from different sources or source combinations into different ChemVol (CV) samplers in real time using a novel source-oriented sampling technique based on single particle mass spectrometry. We segregated the particles from each source-oriented mixture into two size fractions - ultrafine (Dp ? 0.17 ?m) and submicron fine (0.17 ?m ? Dp ? 1.0 ?m) - and measured metals and the rate of DTT loss in each PM extract. We find that the mass-normalized oxidative potential of different sources varies by up to a actor of 8 and that submicron fine PM typically has a larger mass-normalized oxidative potential than ultrafine PM from the same source. Vehicular Emissions, Regional Source Mix, Commute Hours, Daytime Mixed Layer and Nighttime Inversion sources exhibit the highest mass-normalized oxidative potential. When we apportion the volume-normalized oxidative potential, which also accounts for the source's prevalence, cooking sources account for 18-29% of the total DTT loss while mobile (traffic) sources account for 16-28%. When we apportion DTT activity for total PM sampled to specific chemical compounds, soluble copper accounts for roughly 50% of total air-volume-normalized oxidative potential, soluble manganese accounts for 20%, and other unknown species, likely including quinones and other organics, account for 30%. During nighttime, soluble copper and manganese largely explain the oxidative potential of PM, while daytime has a larger contribution from unknown (likely organic) species.

  13. Creating rigorous pathways to monetize methane and nitrous oxide emission reductions at small scale rice farms in three states of semi-arid peninsular India

    NASA Astrophysics Data System (ADS)

    Kritee, K.; Tiwari, R.; Nair, D.; Adhya, T. K.; Rudek, J.

    2014-12-01

    As a part of a joint undertaking by Environmental Defense Fund and the Fair Climate Network, we have measured reduction in methane and nitrous oxide emissions due to alternate "low carbon" rice cultivation practices for three ago-ecological zones in India for the past two years. Sampling for nitrous oxide and methane emissions was done on approximately 60-80% of the total number of days in a growing season and was based on modified GRACEnet protocol. In recognition of farmer's economic interest and global food security demands, we also measured the effect of rice cultivation practices on farm economics and yields. Our data from three agro-ecological zones for 2012-2014 suggest that, for semi-arid peninsular India, low-carbon rice cultivation practices offer large range of emission reduction potential (0.5-5 metric tons CO2e/acre/year). The regions with sandy soils (Alfisols) had high rates of nitrous oxide emissions even under baseline "flooded" rice cultivation regimes and, thus, the Tier 1 IPCC emissions factors grossly underestimate both the amount of nitrous oxide emission from conventional rice cultivation practices, and the extent to which it can be reduced through better fertilizer management. Also, the IPCC factors overestimate the methane emission reduction possible due to water management for rice paddies. Therefore, it is crucial to customize N and water management to each region such that yields and net GHG emission reduction are maximized. These practices also have the potential to decrease water use by 10-30% and improve long term soil health by optimizing organic matter and increasing water-holding capacity. In addition, through GPS based demarcation of farmer plots, recording baseline practices through extensive surveys, documenting the parameters required to aggregate and prove implementation of low carbon rice farming practices, and to model the GHG emission reduction over large scales, we have put forward a path for better monetization of GHG emission reductions which will incentivize adoption of such practices. The payoff is a "triple win" including increased long-term food security (through enhanced yields), rural economic development (through improved farm profitability and adaptation), and lower environmental impacts (including lower GHG emissions).

  14. Metabolism of halogenated alkanes by cytochrome P450 enzymes. Aerobic oxidation versus anaerobic reduction.

    PubMed

    Ji, Li; Zhang, Jing; Liu, Weiping; de Visser, Sam P

    2014-04-01

    The cytochromes P450 are a large class of heme-containing enzymes that catalyze a broad range of chemical reactions in biosystems, mainly through oxygen-atom transfer to substrates. A relatively unknown reaction catalyzed by the P450s, but very important for human health, is the activation of halogenated substrates, which may lead to toxicity problems. However, its catalytic mechanism is currently unknown and, therefore, we performed a detailed computational study. To gain insight into the metabolism of halogenated compounds by P450 enzymes, we have investigated the oxidative and reductive P450-mediated activation of tetra- and trichloromethane as halogenated models with density functional theory (DFT) methods. We propose an oxidative halosylation mechanism for CCl4 under aerobic conditions by Compound?I of P450, which follows the typical Groves-type rebound mechanism. By contrast, the metabolism of CHCl3 occurs preferentially via an initial hydrogen-atom abstraction rather than halosylation. Kinetic isotope effect studies should, therefore, be able to distinguish the mechanistic pathways of CCl4 versus CHCl3 . We find a novel mechanism that is different from the well accepted P450 substrate activation mechanisms reported previously. Moreover, the studies highlight the substrate specific activation pathways by P450 enzymes leading to different products. These reactivity differences are rationalized using Marcus theory equations, which reproduce experimental product distributions. PMID:24501011

  15. Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Littrell, D. M.; Tatarchuk, B. J.

    1986-01-01

    The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

  16. POTENTIAL OF GREENHOUSE GASES REDUCTION BY FUEL CROP CULTIVATION UTILIZING SEWAGE SLUDGE IN JAPAN

    NASA Astrophysics Data System (ADS)

    Honda, Ryo; Fukushi, Kensuke

    Potential of greenhouse gases (GHG) reduction was estimated and compared in six scenarios of fuel crop cultivation by utilizing sewage sludge in Japan. Bioethanol from corn and biodiesel fuel from soybean was selected as biofuel produced. When all the sludge discharged from sewage treatment plants in 18 major cities was utilized for soybean cultivation and subsequent biodiesel fuel production, produced biofuel corresponded to 4.0% of GHG emitted from sewage treatment in Japan. On the other hand, cultivation area for fuel crop cultivation was found to be the regulating factor. When fuel crop was cultivated only in abandoned agricultural fields, produced biofuel corresponded to 0.60% and 0.62%, respectively, in the case that corn and soybean was cultivated. Production of biodiesel fuel from soybean was estimated to have more net reduction potential than bioehanol production from corn when sludge production is limited, because required sewage sludge compost was 2.5-times larger in corn although reduction potential per crop area was 2-times larger in bioethanol production from corn.

  17. Dual enhancement-inhibition roles of polycarboxylates in Cr(VI) reduction and organic pollutant oxidation in electrical plasma system.

    PubMed

    Jiang, Bo; Wang, Xianli; Hu, Ping; Wu, Mingbo; Zheng, Jingtang; Wu, Wenting

    2016-02-01

    In this study, the roles of polycarboxylates in synergistic Cr(VI) reduction and organic pollutant oxidation are investigated in glow discharge electrolysis (GDE). H2O2 generated in GDE plays a primary role for Cr(VI) reduction, and the presence of polycarboxylates can significantly enhance the reduction of Cr(VI) to Cr(III) with less value of [H2O2]consumption/[Cr(VI)]reduction. Simultaneously, polycarboxylates inhibit the production of OH via chromium-based Fenton-like reaction, leading to the retarded oxidation of other pollutant oxidation, i.e., RhB. The formation of peroxochromate(V) is a requisite both for Cr(VI) reduction to Cr(III) and OH formation via Fenton-like reaction. Polycarboxylates can form complexes with peroxochromate(V), which can transform to Cr(III) spontaneously, thereby interrupting the pathway for additional OH production. These influences induced by polycarboxylate were found closely relative to the number and position of -OH group in polycarboxylates. Besides, 162.7 mg L(-1) Cr(VI) in actual electroplating effluent can be rapidly and almost completely reduced in GDE with introducing polycarboxylate containing nickel electroplating effluent. Generally, the present study provides a versatile strategy for Cr(VI) reduction, exhibiting a bright application future for real wastewater treatment. PMID:26517389

  18. Cell toxicity and oxidative potential of engine exhaust particles: impact of using particulate filter or biodiesel fuel blend.

    PubMed

    Gerlofs-Nijland, Miriam E; Totlandsdal, Annike I; Tzamkiozis, Theodoros; Leseman, Daan L A C; Samaras, Zissis; Låg, Marit; Schwarze, Per; Ntziachristos, Leonidas; Cassee, Flemming R

    2013-06-01

    The link between emissions of vehicular particulate matter (PM) and adverse health effects is well established. However, the influence of new emission control technologies and fuel types on both PM emissions and health effects has been less well investigated. We examined the health impact of PM emissions from two vehicles equipped with or without a diesel particulate filter (DPF). Both vehicles were powered either with diesel (B0) or a 50% v/v biodiesel blend (B50). The DPF effectively decreased PM mass emissions (?85%), whereas the fuel B50 without DPF lead to less reduction (?50%). The hazard of PM per unit distance driven was decreased for the DPF-equipped vehicle as indicated by a reduced cytotoxicity, oxidative, and pro-inflammatory potential. This was not evident and even led to an increase when the hazard was expressed on a per unit of mass basis. In general, the PM oxidative potential was similar or reduced for the B50 compared to the B0 powered vehicle. However, the use of B50 resulted in increased cytotoxicity and IL-6 release in BEAS-2B cells irrespective of the expression metric. This study shows that PM mass reduction achieved by the use of B50 will not necessarily decrease the hazard of engine emissions, while the application of a DPF has a beneficial effect on both PM mass emission and PM hazard. PMID:23597117

  19. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases

    DOEpatents

    Sobolevskiy, Anatoly; Rossin, Joseph A

    2014-04-08

    A multi-stage selective catalytic reduction (SCR) unit (32) provides efficient reduction of NOx and other pollutants from about 50-550.degree. C. in a power plant (19). Hydrogen (24) and ammonia (29) are variably supplied to the SCR unit depending on temperature. An upstream portion (34) of the SCR unit catalyzes NOx+NH.sub.3 reactions above about 200.degree. C. A downstream portion (36) catalyzes NOx+H.sub.2 reactions below about 260.degree. C., and catalyzes oxidation of NH.sub.3, CO, and VOCs with oxygen in the exhaust above about 200.degree. C., efficiently removing NOx and other pollutants over a range of conditions with low slippage of NH.sub.3. An ammonia synthesis unit (28) may be connected to the SCR unit to provide NH.sub.3 as needed, avoiding transport and storage of ammonia or urea at the site. A carbonaceous gasification plant (18) on site may supply hydrogen and nitrogen to the ammonia synthesis unit, and hydrogen to the SCR unit.

  20. Diverse syntrophic relationships within a microbial community performing anaerobic oxidation of methane and sulfate reduction

    NASA Astrophysics Data System (ADS)

    Wang, F.; Chen, Y.; Zhang, Y.; He, Y.; Xiao, X.

    2012-12-01

    Here we report the metagenome and metatranscriptome analysis of a highly enriched, active AOM-SR (anaerobic oxidation of methane - sulfate reduction) community obtained through a continuous high-pressure bioreactor system. The community has a very high diversity of bacteria, besides SRB within delta-Proteobacteria, gamma-, beta-Proteobacteria and OP1 were found abundant. The archaeal components in the system are rather simple with only ANME2 and Marine Benthic Group D detected. FISH analysis revealed that most ANME cells form cell aggregates with SRB. A complete and functioning methanogenesis pathway from CO2 reduction was identified. Besides the methanogenesis and sulfate reducing pathways, pathways for complete denitrification and nitrogen fixation were also identified and expressed. Single cell aggregates in the community were captured and sequenced. Besides ANME and SRB, a third type of microorganisms were found present in certain cell aggregates, thus provide direct evidence for diverse syntrophic relationships among the microorganisms within the system fueled by AOM-SR.

  1. Reduction of graphene oxide/alginate composite hydrogels for enhanced adsorption of hydrophobic compounds

    NASA Astrophysics Data System (ADS)

    Kim, Semin; Yoo, Youngjae; Kim, Hanbit; Lee, Eunji; Lee, Jae Young

    2015-10-01

    Carbon-based materials, consisting of graphene oxide (GO) or reduced GO (rGO), possess unique abilities to interact with various molecules. In particular, rGO materials hold great promise for adsorption and delivery applications of hydrophobic molecules. However, conventional production and/or usage of rGO in aqueous solution often causes severe aggregation due to its low water solubility and thus difficulties in handling and applications. In our study, to prevent the severe aggregation of GO during reduction and to achieve a high adsorption capacity with hydrophobic compounds, GO/alginate composite hydrogels were first prepared and then reduced in an aqueous ascorbic acid solution at 37 °C. Adsorption studies with a model hydrophobic substance, rhodamine B, revealed that the reduced composite hydrogels are more highly absorbent than the unreduced hydrogels. In addition, the adsorption properties of the composite hydrogels, which are consequences of hydrophobic and ionic interactions, could be modulated by controlling the degree of reduction for the adsorption of different molecules. The composite hydrogels embedding rGO can be very useful in applications related to drug delivery, waste treatment, and biosensing.

  2. The potential for biologically catalyzed anaerobic methane oxidation on ancient Mars.

    PubMed

    Marlow, Jeffrey J; Larowe, Douglas E; Ehlmann, Bethany L; Amend, Jan P; Orphan, Victoria J

    2014-04-01

    This study examines the potential for the biologically mediated anaerobic oxidation of methane (AOM) coupled to sulfate reduction on ancient Mars. Seven distinct fluids representative of putative martian groundwater were used to calculate Gibbs energy values in the presence of dissolved methane under a range of atmospheric CO2 partial pressures. In all scenarios, AOM is exergonic, ranging from -31 to -135 kJ/mol CH4. A reaction transport model was constructed to examine how environmentally relevant parameters such as advection velocity, reactant concentrations, and biomass production rate affect the spatial and temporal dependences of AOM reaction rates. Two geologically supported models for ancient martian AOM are presented: a sulfate-rich groundwater with methane produced from serpentinization by-products, and acid-sulfate fluids with methane from basalt alteration. The simulations presented in this study indicate that AOM could have been a feasible metabolism on ancient Mars, and fossil or isotopic evidence of this metabolic pathway may persist beneath the surface and in surface exposures of eroded ancient terrains. PMID:24684241

  3. Agricultural conservation planning framework: 1. Developing multipractice watershed planning scenarios and assessing nutrient reduction potential.

    PubMed

    Tomer, M D; Porter, S A; Boomer, K M B; James, D E; Kostel, J A; Helmers, M J; Isenhart, T M; McLellan, E

    2015-05-01

    Spatial data on soils, land use, and topography, combined with knowledge of conservation effectiveness, can be used to identify alternatives to reduce nutrient discharge from small (hydrologic unit code [HUC]12) watersheds. Databases comprising soil attributes, agricultural land use, and light detection and ranging-derived elevation models were developed for two glaciated midwestern HUC12 watersheds: Iowa's Beaver Creek watershed has an older dissected landscape, and Lime Creek in Illinois is young and less dissected. Subsurface drainage is common in both watersheds. We identified locations for conservation practices, including in-field practices (grassed waterways), edge-of-field practices (nutrient-removal wetlands, saturated buffers), and drainage-water management, by applying terrain analyses, geographic criteria, and cross-classifications to field- and watershed-scale geographic data. Cover crops were randomly distributed to fields without geographic prioritization. A set of alternative planning scenarios was developed to represent a variety of extents of implementation among these practices. The scenarios were assessed for nutrient reduction potential using a spreadsheet approach to calculate the average nutrient-removal efficiency required among the practices included in each scenario to achieve a 40% NO-N reduction. Results were evaluated in the context of the Iowa Nutrient Reduction Strategy, which reviewed nutrient-removal efficiencies of practices and established the 40% NO-N reduction as Iowa's target for Gulf of Mexico hypoxia mitigation by agriculture. In both test watersheds, planning scenarios that could potentially achieve the targeted NO-N reduction but remove <5% of cropland from production were identified. Cover crops and nutrient removal wetlands were common to these scenarios. This approach provides an interim technology to assist local watershed planning and could provide planning scenarios to evaluate using watershed simulation models. A set of ArcGIS tools is being released to enable transfer of this mapping technology. PMID:26024256

  4. Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N,N-Dimethylformamide.

    PubMed

    Pegis, Michael L; Roberts, John A S; Wasylenko, Derek J; Mader, Elizabeth A; Appel, Aaron M; Mayer, James M

    2015-12-21

    A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e(-) + 4H(+) ? 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc(+/0)) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water from aqueous solution to organic solvent, -0.43 kcal mol(-1) for MeCN and -1.47 kcal mol(-1) for DMF, and the potential of the H(+)/H2 couple, - 0.028 V in MeCN and -0.662 V in DMF. The H(+)/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol(-1) for acetonitrile and +0.6 kcal mol(-1) for DMF. PMID:26640971

  5. Three-dimensional patterning of solid microstructures through laser reduction of colloidal graphene oxide in liquid-crystalline dispersions

    NASA Astrophysics Data System (ADS)

    Senyuk, Bohdan; Behabtu, Natnael; Martinez, Angel; Lee, Taewoo; Tsentalovich, Dmitri E.; Ceriotti, Gabriel; Tour, James M.; Pasquali, Matteo; Smalyukh, Ivan I.

    2015-05-01

    Graphene materials and structures have become an essential part of modern electronics and photovoltaics. However, despite many production methods, applications of graphene-based structures are hindered by high costs, lack of scalability and limitations in spatial patterning. Here we fabricate three-dimensional functional solid microstructures of reduced graphene oxide in a lyotropic nematic liquid crystal of graphene oxide flakes using a pulsed near-infrared laser. This reliable, scalable approach is mask-free, does not require special chemical reduction agents, and can be implemented at ambient conditions starting from aqueous graphene oxide flakes. Orientational ordering of graphene oxide flakes in self-assembled liquid-crystalline phases enables laser patterning of complex, three-dimensional reduced graphene oxide structures and colloidal particles, such as trefoil knots, with `frozen' orientational order of flakes. These structures and particles are mechanically rigid and range from hundreds of nanometres to millimetres in size, as needed for applications in colloids, electronics, photonics and display technology.

  6. Plasma Protein Oxidation and Its Correlation with Antioxidant Potential During Human Aging

    PubMed Central

    Pandey, Kanti Bhooshan; Mehdi, Mohd Murtaza; Maurya, Pawan Kumar; Rizvi, Syed Ibrahim

    2010-01-01

    Previous studies have indicated that the main molecular characteristic of aging is the progressive accumulation of oxidative damages in cellular macromolecules. Proteins are one of the main molecular targets of age-related oxidative stress, which have been observed during aging process in cellular systems. Reactive oxygen species (ROS) can lead to oxidation of amino acid side chains, formation of protein-protein cross-linkages, and oxidation of the peptide backbones. In the present study, we report the age-dependent oxidative alterations in biomarkers of plasma protein oxidation: protein carbonyls (PCO), advanced oxidation protein products (AOPPs) and plasma total thiol groups (T-SH) in the Indian population and also correlate these parameters with total plasma antioxidant potential. We show an age dependent decrease in T-SH levels and increase in PCO and AOPPs level. The alterations in the levels of these parameters correlated significantly with the total antioxidant capacity of the plasma. The levels of oxidized proteins in plasma provide an excellent biomarker of oxidative stress due to the relative long half-life of such oxidized proteins. PMID:20826915

  7. The reduction of graphene oxide with hydrazine: elucidating its reductive capability based on a reaction-model approach.

    PubMed

    Chua, Chun Kiang; Pumera, Martin

    2015-12-15

    We have performed an experimental investigation on the effects of hydrazine treatment on graphene oxide via a reaction-model approach. Hydrazine was reacted with small conjugated aromatic compounds containing various oxygen functional groups to mimic the structure of graphene oxide. The hydroxyl and carboxylic groups were not readily removed while carbonyl groups reacted with hydrazine to form the corresponding hydrazone complexes. In the presence of adjacent hydroxyl groups, carboxyl groups underwent thermal decarboxylation. PMID:26525927

  8. Temperature dependence of the reduction potential of CuA in carbon monoxide inhibited cytochrome c oxidase.

    PubMed

    Wang, H; Blair, D F; Ellis, W R; Gray, H B; Chan, S I

    1986-01-14

    The temperature dependence of the reduction potential of the CuA site in carbon monoxide inhibited cytochrome c oxidase has been measured with a spectroelectrochemical method adapted to the relatively weak near-infrared absorption of this copper ion. These measurements, together with parallel measurements on the 604-nm absorption due to Fea, indicate that an interaction between CuA and Fea causes the reduction potential for one of these sites to be decreased by approximately 40 mV upon reduction of the other. The temperature dependence of the CuA reduction potential indicates a relatively large and negative standard entropy of reduction of CuA (delta So' = -48.7 +/- 2.3 eu). Possible implications of the intersite redox interaction and the large standard entropy of reduction of the CuA site are discussed. PMID:3006750

  9. A quantum chemical study of nitric oxide reduction by ammonia (SCR reaction) on V2O5 catalyst surface

    E-print Network

    Senkan, Selim M.

    A quantum chemical study of nitric oxide reduction by ammonia (SCR reaction) on V2O5 catalyst surface Sezen Soyer a , Alper Uzun a , Selim Senkan b , Isik Onal a,* a Department of Chemical Engineering, Middle East Technical University, Ankara 06531, Turkey b Department of Chemical Engineering, University

  10. High-Index-Contrast AlGaAs Waveguide Scattering Loss Reduction Via Oxidation Smoothing of Sidewall Roughness

    E-print Network

    are fabricated from an AlGaAs graded-index separate confinement heterostructure grown via MOCVD at SarnoffHigh-Index-Contrast AlGaAs Waveguide Scattering Loss Reduction Via Oxidation Smoothing of Sidewall-6449 Abstract: The propagation loss of single mode high index contrast AlGaAs ridge waveguides is reduced nearly

  11. EVALUATION OF PRIMARY AIR VITIATION FOR NITRIC OXIDE REDUCTION IN A ROTARY CEMENT KILN. VOLUME 1. TECHNICAL REPORT

    EPA Science Inventory

    The report gives results of tests to evaluate combustion modifications for nitric oxide (NO) reduction and cement product quality in a pilot-scale long-dry-process cement kiln firing pulverized coal. The kiln is rated at 11.35 kg/s (1080 tons/day) of cement with a thermal input r...

  12. EVALUATION OF PRIMARY AIR VITIATION FOR NITRIC OXIDE REDUCTION IN A ROTARY CEMENT KILN. VOLUME 2. DATA SUPPLEMENT A

    EPA Science Inventory

    The report gives results of tests to evaluate combustion modifications for nitric oxide (NO) reduction and cement product quality in a pilot-scale long-dry-process cement kiln firing pulverized coal. The kiln is rated at 11.35 kg/s (1080 tons/day) of cement with a thermal input r...

  13. Petrology and Geochemistry of Lunar Regolith Particle 65903,16-7: Evidence for Extreme Reduction and Oxidation

    NASA Technical Reports Server (NTRS)

    Zeigler, R. A.; Jolliff, B. L.; Korotev, R. L.; Kremser, D. T.; Haskin, L. A.

    2001-01-01

    Apollo 16 particle 65903,16-7 is a magnesian, alkali-rich impact melt breccia. Low Fe/Mn and high phosphide/phosphate ratios are evidence of severe reduction during impact-melt cooling. Presence of carbonate and FeOOH is evidence for later oxidation. Additional information is contained in the original extended abstract.

  14. MERCURY OXIDATION PROMOTED BY A SELECTIVE CATALYTIC REDUCTION CATALYST UNDER SIMULATED POWDER RIVER BASIN COAL COMBUSTION CONDITIONS

    EPA Science Inventory

    A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury oxidation under SCR conditions. A low sulfur Power River Basin (PRB) coal combustion ...

  15. An Examination of Drag Reduction Mechanisms in Marine Animals, with Potential Applications to Uninhabited Aerial Vehicles

    NASA Technical Reports Server (NTRS)

    Musick, John A.; Patterson, Mark R.; Dowd, Wesley W.

    2002-01-01

    Previous engineering research and development has documented the plausibility of applying biomimetic approaches to aerospace engineering. Past cooperation between the Virginia Institute of Marine Science (VIMS) and NASA focused on the drag reduction qualities of the microscale dermal denticles of shark skin. This technology has subsequently been applied to submarines and aircraft. The present study aims to identify and document the three-dimensional geometry of additional macroscale morphologies that potentially confer drag reducing hydrodynamic qualities upon marine animals and which could be applied to enhance the range and endurance of Uninhabited Aerial Vehicles (UAVs). Such morphologies have evolved over eons to maximize organismal energetic efficiency by reducing the energetic input required to maintain cruising speeds in the viscous marine environment. These drag reduction qualities are manifested in several groups of active marine animals commonly encountered by ongoing VIMS research programs: namely sharks, bony fishes such as tunas, and sea turtles. Through spatial data acquired by molding and digital imagery analysis of marine specimens provided by VIMS, NASA aims to construct scale models of these features and to test these potential drag reduction morphologies for application to aircraft design. This report addresses the efforts of VIMS and NASA personnel on this project between January and November 2001.

  16. Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile

    SciTech Connect

    Roberts, John A.; Bullock, R. Morris

    2013-03-14

    Open circuit potentials were measured for acetonitrile solutions of a variety of acids and their conjugate bases under 1 atm H2. Acids examined include triethylammonium, dimethylformamidium, 2,6-dichloroanilinium, 4-cyanoanilinium, 4-bromoanilinium, and 4-anisidinium salts. These potentials, together with the pKa values of the acids, establish the value of the standard hydrogen electrode (SHE) potential in acetonitrile as ?0.028(4) V vs the ferrocenium/ferrocene couple. Dimethylformamidium is shown to form homoconjugates and other aggregates with dimethylformamide; open circuit potentials are used to quantify the extent of these reactions. Overpotentials for electrocatalytic hydrogen production and oxidation were determined from open circuit potentials and voltammograms of acidic or basic catalyst solutions under H2. This method requires neither pKa values, homoconjugation constants, nor an estimate for the SHE potential and thus allows direct comparison of catalytic systems in different media.

  17. Soil Oxidation-Reduction in Wetlands and Its Impact on Plant Functioning

    PubMed Central

    Pezeshki, S. R.; DeLaune, R. D.

    2012-01-01

    Soil flooding in wetlands is accompanied by changes in soil physical and chemical characteristics. These changes include the lowering of soil redox potential (Eh) leading to increasing demand for oxygen within the soil profile as well as production of soil phytotoxins that are by-products of soil reduction and thus, imposing potentially severe stress on plant roots. Various methods are utilized for quantifying plant responses to reducing soil conditions that include measurement of radial oxygen transport, plant enzymatic responses, and assessment of anatomical/morphological changes. However, the chemical properties and reducing nature of soil environment in which plant roots are grown, including oxygen demand, and other associated processes that occur in wetland soils, pose a challenge to evaluation and comparison of plant responses that are reported in the literature. This review emphasizes soil-plant interactions in wetlands, drawing attention to the importance of quantifying the intensity and capacity of soil reduction for proper evaluation of wetland plant responses, particularly at the process and whole-plant levels. Furthermore, while root oxygen-deficiency may partially account for plant stress responses, the importance of soil phytotoxins, produced as by-products of low soil Eh conditions, is discussed and the need for development of methods to allow differentiation of plant responses to reduced or anaerobic soil conditions vs. soil phytotoxins is emphasized. PMID:24832223

  18. Particle emissions from microalgae biodiesel combustion and their relative oxidative potential.

    PubMed

    Rahman, M M; Stevanovic, S; Islam, M A; Heimann, K; Nabi, M N; Thomas, G; Feng, B; Brown, R J; Ristovski, Z D

    2015-09-01

    Microalgae are considered to be one of the most viable biodiesel feedstocks for the future due to their potential for providing economical, sustainable and cleaner alternatives to petroleum diesel. This study investigated the particle emissions from a commercially cultured microalgae and higher plant biodiesels at different blending ratios. With a high amount of long carbon chain lengths fatty acid methyl esters (C20 to C22), the microalgal biodiesel used had a vastly different average carbon chain length and level of unsaturation to conventional biodiesel, which significantly influenced particle emissions. Smaller blend percentages showed a larger reduction in particle emission than blend percentages of over 20%. This was due to the formation of a significant nucleation mode for the higher blends. In addition measurements of reactive oxygen species (ROS), showed that the oxidative potential of particles emitted from the microalgal biodiesel combustion were lower than that of regular diesel. Biodiesel oxygen content was less effective in suppressing particle emissions for biodiesels containing a high amount of polyunsaturated C20-C22 fatty acid methyl esters and generated significantly increased nucleation mode particle emissions. The observed increase in nucleation mode particle emission is postulated to be caused by very low volatility, high boiling point and high density, viscosity and surface tension of the microalgal biodiesel tested here. Therefore, in order to achieve similar PM (particulate matter) emission benefits for microalgal biodiesel likewise to conventional biodiesel, fatty acid methyl esters (FAMEs) with high amounts of polyunsaturated long-chain fatty acids (?C20) may not be desirable in microalgal biodiesel composition. PMID:26238214

  19. Oxygen potential of a prototypic Mo-cermet fuel containing plutonium oxide

    NASA Astrophysics Data System (ADS)

    Miwa, Shuhei; Osaka, Masahiko; Nozaki, Takahiro; Arima, Tatsumi; Idemitsu, Kazuya

    2015-10-01

    Oxygen potential of a prototypic Mo-cermet fuel containing 50 vol.% PuO2-x were investigated by the thermogravimetric analysis in the temperature range from 1273 K to 1473 K. It was shown that the oxygen potential and oxidation rate of the Mo-cermet were the same as those of pure PuO2-x below the oxygen potential of Mo/MoO2 oxidation reaction. The same features of the Mo-cermet sample containing 50 vol.% PuO2-x with those of pure PuO2-x were discussed in terms of the microstructure.

  20. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    NASA Astrophysics Data System (ADS)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ? E ? Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  1. AUTO-OXIDATION POTENTIAL OF RAW AND RETORTED OIL SHALE

    EPA Science Inventory

    This paper discusses an EPA sponsored study to assess the potential environmental impacts of leachates from raw mined western oil shales. The study was undertaken as a cooperative effort of the Environmental Protection Agency, Colorado State University, Rio Blanco Oil Shale Compa...

  2. Potential Impacts of Drainage Management on Nitrous Oxide Emissions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Artificial drainage is an essential component of agricultural production in many regions of the U.S., but it can increase the export of nitrogen (primarily as nitrate) and other nutrients from fields to water bodies. Several management practices have the potential to remove nitrate from water eithe...

  3. Molecular oxygen reduction catalyzed by a highly oxidative resistant complex of cobalt-hydrazone at the liquid/liquid interface.

    PubMed

    Kamyabi, Mohammad Ali; Soleymani-Bonoti, Fatemeh; Bikas, Rahman; Hosseini-Monfared, Hassan; Arshadi, Nematollah; Siczek, Milosz; Lis, Tadeusz

    2015-12-01

    A new complex of Co(iii) using an oxidative stable hydrazone ligand, CoL, was synthesized and characterized by elemental analysis, spectroscopic methods and single crystal X-ray analysis where HL is bis-[(E)-N'-(phenyl(pyridin-2-yl)methylene)]carbohydrazide. X-ray analysis revealed that the complex is mononuclear and the coordination environment around the Co(iii) core is trans-[CoN4Cl2]. The catalytic activity of the complex in the oxygen reduction reaction was investigated. The complex is a highly oxidative resistant cobalt-hydrazone which can efficiently catalyze the reduction of oxygen (O2) by a weak electron donor ferrocene, (Fc), at the polarized water/1,2-dichloroethane (DCE) interface. Oxygen reduction is coupled with proton transfer from water to the organic phase to form hydrogen peroxide, which is extracted into the aqueous phase. PMID:26377052

  4. Twitter as a Potential Disaster Risk Reduction Tool. Part I: Introduction, Terminology, Research and Operational Applications

    PubMed Central

    Cooper, Guy Paul; Yeager, Violet; Burkle, Frederick M.; Subbarao, Italo

    2015-01-01

    Twitter, a popular communications platform, is identified as contributing to improved mortality and morbidity outcomes resulting from the 2013 Hattiesburg, Mississippi EF-4 Tornado. This study describes the methodology by which Twitter was investigated as a potential disaster risk reduction and management tool at the community level and the process by which the at-risk population was identified from the broader Twitter user population. By understanding how various factors contribute to the superspreading of messages, one can better optimize Twitter as an essential communications and risk reduction tool. This study introduces Parts II, III and IV which further define the technological and scientific knowledge base necessary for developing future competency base curriculum and content for Twitter assisted disaster management education and training at the community level.  PMID:26203395

  5. Twitter as a Potential Disaster Risk Reduction Tool. Part I: Introduction, Terminology, Research and Operational Applications.

    PubMed

    Cooper, Guy Paul; Yeager, Violet; Burkle, Frederick M; Subbarao, Italo

    2015-01-01

    Twitter, a popular communications platform, is identified as contributing to improved mortality and morbidity outcomes resulting from the 2013 Hattiesburg, Mississippi EF-4 Tornado. This study describes the methodology by which Twitter was investigated as a potential disaster risk reduction and management tool at the community level and the process by which the at-risk population was identified from the broader Twitter user population. By understanding how various factors contribute to the superspreading of messages, one can better optimize Twitter as an essential communications and risk reduction tool. This study introduces Parts II, III and IV which further define the technological and scientific knowledge base necessary for developing future competency base curriculum and content for Twitter assisted disaster management education and training at the community level. PMID:26203395

  6. Pentoxifylline decreases oxidized lipid products in nonalcoholic steatohepatitis: New evidence on the potential therapeutic mechanism

    PubMed Central

    Zein, Claudia O.; Lopez, Rocio; Fu, Xiaoming; Kirwan, John P.; Yerian, Lisa M.; McCullough, Arthur J.; Hazen, Stanley L.; Feldstein, Ariel E.

    2012-01-01

    Background Pentoxifylline (PTX) improved histological features of nonalcoholic steatohepatitis (NASH) in a recent randomized placebo-controlled trial. However, the underlying mechanism responsible for the beneficial effects of PTX in NASH remains unidentified. A key role of lipid oxidation in the pathogenesis and progression of NASH has been established. PTX is known to decrease free-radical mediated oxidative stress and inhibit lipid oxidation. The primary aim of this study was to evaluate the effects of PTX on levels of lipid oxidation products in patients with NASH. Methods Levels of multiple structurally specific oxidized fatty acids including hydroxy-octadecadenoic acids (HODEs), oxo-octadecadenoic acids (oxoODEs), and hydroxy-eicosatetraenoic acids (HETEs) were quantified by mass spectrometry in plasma obtained at baseline and at study completion in patients who completed 1 year of therapy with PTX or placebo in a randomized controlled trial. Results Therapy with PTX resulted in significant decreases on 9-HODE and 13-oxoODE, oxidized lipid products of linoleic acid (LA) linked to histological severity in NAFLD. Similarly, PTX therapy was associated with significant decreases in 8-HETE, 9-HETE, and 11-HETE compared to placebo. Statistically significant correlations were demonstrated between the decrease in HODEs and oxoODEs and improved histological scores of fibrosis; and between the decrease in HETEs and improved lobular inflammation. Conclusion Therapy with PTX compared to placebo was associated with a significant reduction of oxidized fatty acids. This novel evidence supports that the beneficial effects of PTX in patients with NASH are likely partly mediated through decreasing lipid oxidation, largely free-radical mediated lipid oxidation. Additionally, this is the first report on the link between decreased oxidized lipid products and improved histological disease in the setting of a therapeutic trial in NASH. PMID:22505276

  7. GREENHOUSE GAS REDUCTION POTENTIAL WITH COMBINED HEAT AND POWER WITH DISTRIBUTED GENERATION PRIME MOVERS - ASME 2012

    SciTech Connect

    Curran, Scott; Theiss, Timothy J; Bunce, Michael

    2012-01-01

    Pending or recently enacted greenhouse gas regulations and mandates are leading to the need for current and feasible GHG reduction solutions including combined heat and power (CHP). Distributed generation using advanced reciprocating engines, gas turbines, microturbines and fuel cells has been shown to reduce greenhouse gases (GHG) compared to the U.S. electrical generation mix due to the use of natural gas and high electrical generation efficiencies of these prime movers. Many of these prime movers are also well suited for use in CHP systems which recover heat generated during combustion or energy conversion. CHP increases the total efficiency of the prime mover by recovering waste heat for generating electricity, replacing process steam, hot water for buildings or even cooling via absorption chilling. The increased efficiency of CHP systems further reduces GHG emissions compared to systems which do not recover waste thermal energy. Current GHG mandates within the U.S Federal sector and looming GHG legislation for states puts an emphasis on understanding the GHG reduction potential of such systems. This study compares the GHG savings from various state-of-the- art prime movers. GHG reductions from commercially available prime movers in the 1-5 MW class including, various industrial fuel cells, large and small gas turbines, micro turbines and reciprocating gas engines with and without CHP are compared to centralized electricity generation including the U.S. mix and the best available technology with natural gas combined cycle power plants. The findings show significant GHG saving potential with the use of CHP. Also provided is an exploration of the accounting methodology for GHG reductions with CHP and the sensitivity of such analyses to electrical generation efficiency, emissions factors and most importantly recoverable heat and thermal recovery efficiency from the CHP system.

  8. Minimizing noise in fiberglass aquaculture tanks: Noise reduction potential of various retrofits

    USGS Publications Warehouse

    Davidson, J.; Frankel, A.S.; Ellison, W.T.; Summerfelt, S.; Popper, A.N.; Mazik, P.; Bebak, J.

    2007-01-01

    Equipment used in intensive aquaculture systems, such as pumps and blowers can produce underwater sound levels and frequencies within the range of fish hearing. The impacts of underwater noise on fish are not well known, but limited research suggests that subjecting fish to noise could result in impairment of the auditory system, reduced growth rates, and increased stress. Consequently, reducing sound in fish tanks could result in advantages for cultured species and increased productivity for the aquaculture industry. The objective of this study was to evaluate the noise reduction potential of various retrofits to fiberglass fish culture tanks. The following structural changes were applied to tanks to reduce underwater noise: (1) inlet piping was suspended to avoid contact with the tank, (2) effluent piping was disconnected from a common drain line, (3) effluent piping was insulated beneath tanks, and (4) tanks were elevated on cement blocks and seated on insulated padding. Four combinations of the aforementioned structural changes were evaluated in duplicate and two tanks were left unchanged as controls. Control tanks had sound levels of 120.6 dB re 1 ??Pa. Each retrofit contributed to a reduction of underwater sound. As structural changes were combined, a cumulative reduction in sound level was observed. Tanks designed with a combination of retrofits had sound levels of 108.6 dB re 1 ??Pa, a four-fold reduction in sound pressure level. Sound frequency spectra indicated that the greatest sound reductions occurred between 2 and 100 Hz and demonstrated that nearby pumps and blowers created tonal frequencies that were transmitted into the tanks. The tank modifications used during this study were simple and inexpensive and could be applied to existing systems or considered when designing aquaculture facilities. ?? 2007 Elsevier B.V. All rights reserved.

  9. Reduction of iron-oxide-carbon composites: part II. Rates of reduction of composite pellets in a rotary hearth furnace simulator

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept is being proposed that involves the combination of a rotary hearth furnace (RHF) with an iron-bath smelter. The RHF makes use of iron-oxide-carbon composite pellets as the charge material and the final product is direct-reduced iron (DRI) in the solid or molten state. This part of the research includes the development of a reactor that simulated the heat transfer in an RHF. The external heat-transport and high heating rates were simulated by means of infrared (IR) emitting lamps. The reaction rates were measured by analyzing the off-gas and computing both the amount of CO and CO{sub 2} generated and the degree of reduction. The reduction times were found to be comparable to the residence times observed in industrial RHFs. Both artificial ferric oxide (PAH) and naturally occurring hematite and taconite ores were used as the sources of iron oxide. Coal char and devolatilized wood charcoal were the reductants. Wood charcoal appeared to be a faster reductant than coal char. However, in the PAH-containing pellets, the reverse was found to be true because of heat-transfer limitations. For the same type of reductant, hematite-containing pellets were observed to reduce faster than taconite-containing pellets because of the development of internal porosity due to cracking and fissure formation during the Fe2O{sub 3}-to-Fe3O{sub 4} transition. This is, however, absent during the reduction of taconite, which is primarily Fe3O{sub 4}. The PAH-wood-charcoal pellets were found to undergo a significant amount of swelling at low-temperature conditions, which impeded the external heat transport to the lower layers. If the average degree of reduction targeted in an RHF is reduced from 95 to approximately 70 pct by coupling the RHF with a bath smelter, the productivity of the RHF can be enhanced 1.5 to 2 times. The use of a two- or three-layer bed was found to be superior to that of a single layer, for higher productivities.

  10. Reduction of Iron-Oxide-Carbon Composites: Part II. Rates of Reduction of Composite Pellets in a Rotary Hearth Furnace Simulator

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept is being proposed that involves the combination of a rotary hearth furnace (RHF) with an iron-bath smelter. The RHF makes use of iron-oxide-carbon composite pellets as the charge material and the final product is direct-reduced iron (DRI) in the solid or molten state. This part of the research includes the development of a reactor that simulated the heat transfer in an RHF. The external heat-transport and high heating rates were simulated by means of infrared (IR) emitting lamps. The reaction rates were measured by analyzing the off-gas and computing both the amount of CO and CO2 generated and the degree of reduction. The reduction times were found to be comparable to the residence times observed in industrial RHFs. Both artificial ferric oxide (PAH) and naturally occurring hematite and taconite ores were used as the sources of iron oxide. Coal char and devolatilized wood charcoal were the reductants. Wood charcoal appeared to be a faster reductant than coal char. However, in the PAH-containing pellets, the reverse was found to be true because of heat-transfer limitations. For the same type of reductant, hematite-containing pellets were observed to reduce faster than taconite-containing pellets because of the development of internal porosity due to cracking and fissure formation during the Fe2O3-to-Fe3O4 transition. This is, however, absent during the reduction of taconite, which is primarily Fe3O4. The PAH-wood-charcoal pellets were found to undergo a significant amount of swelling at low-temperature conditions, which impeded the external heat transport to the lower layers. If the average degree of reduction targeted in an RHF is reduced from 95 to approximately 70 pct by coupling the RHF with a bath smelter, the productivity of the RHF can be enhanced 1.5 to 2 times. The use of a two- or three-layer bed was found to be superior to that of a single layer, for higher productivities.

  11. Soot oxidation and NO{sub x} reduction over BaAl{sub 2}O{sub 4} catalyst

    SciTech Connect

    Lin, He; Li, Yingjie; Shangguan, Wenfeng; Huang, Zhen

    2009-11-15

    This study addresses soot oxidation and NO{sub x} reduction over a BaAl{sub 2}O{sub 4} catalyst. By XRD analysis, the catalyst was shown to be of spinel structure. Temperature Programmed Oxidation (TPO) and Constant Temperature Oxidation (CTO) at 673 K show that the presence of O{sub 2} decreases the ignition temperature of soot, and it enhances the conversion of NO{sub x} to N{sub 2} and N{sub 2}O. The kinetic features of soot oxidation in the TPO test are similar to that in the TG-DTA analysis. Analysis by Diffuse Reflectance Fourier Infrared Transform Spectroscopy (DRIFTS) indicates that the nitrates formed from NO{sub x} adsorption and the C(O) intermediates from soot oxidation are the key precursors of the redox process between soot and NO{sub x} over surfaces of the BaAl{sub 2}O{sub 4} catalyst. Moreover, DRIFTS tests suggest that nitrates act as the principal oxidants for C(O) oxidation, through which nitrates are reduced to N{sub 2} and N{sub 2}O. The O{sub 2} in the gas mixture presents a positive effect on the conversion of NO{sub x} to N{sub 2} and N{sub 2}O by promoting the oxidation of nitrites into nitrates species. (author)

  12. POLYCHLORINATED BIPHENYL-INDUCED OXIDATIVE STRESS IN ORGANOTYPIC CO-CULTURES: EXPERIMENTAL DOPAMINE DEPLETION PREVENTS REDUCTIONS IN GABA

    PubMed Central

    Lyng, Gregory D.; Seegal, Richard F.

    2008-01-01

    Polychlorinated biphenyls (PCBs) are ubiquitous environmental contaminants that have been demonstrated to be toxic to the dopamine (DA) systems of the central nervous system. One proposed mechanism for PCB-induced DA neurotoxicity is inhibition of the vesicular monoamine transporter (VMAT); such inhibition results in increased levels of unsequestered DA and DA metabolism leading to oxidative stress. We have used an organotypic co-culture system of developing rat striatum and ventral mesencephalon (VM) to determine whether alterations in the vesicular storage of DA, resulting from PCB exposure and consequent induction of oxidative stress, leads to GABA and DA neuronal dysfunction. 24 hr exposure to an environmentally relevant mixture of PCBs reduced tissue DA and GABA concentrations, increased medium levels of DA and measures of oxidative stress in both the striatum and VM. Alterations in neurochemistry and increases in measures of oxidative stress were blocked in the presence of n-acetylcysteine (NAC). Although NAC treatment did not alter PCB-induced changes in DA neurochemistry, it did protect against reductions in GABA concentration. To determine whether alterations in the vesicular storage of DA were responsible for PCB-induced oxidative stress and consequent reductions in GABA levels, we depleted DA from the co-cultures using ?-methyl-p-tyrosine (AMPT). AMPT reduced striatal and VM DA levels by 90% and 70%, respectively. PCB exposure, following DA depletion, neither increased levels of oxidative stress nor resulted in GABA depletion. These results suggest that PCB-induced alterations in the vesicular storage of DA, resulting in increased levels of unsequestered DA, leads to increased oxidative stress, depletion of tissue glutathione, and consequent reductions in tissue GABA concentrations. PMID:18262273

  13. Microaerophilic Cooperation of Reductive and Oxidative Pathways Allows Maximal Photosynthetic Membrane Biosynthesis in Rhodospirillum rubrum

    PubMed Central

    Grammel, Hartmut; Gilles, Ernst-Dieter; Ghosh, Robin

    2003-01-01

    The purple nonsulfur bacterium Rhodospirillum rubrum has been employed to study physiological adaptation to limiting oxygen tensions (microaerophilic conditions). R. rubrum produces maximal levels of photosynthetic membranes when grown with both succinate and fructose as carbon sources under microaerophilic conditions in comparison to the level (only about 20% of the maximum) seen in the absence of fructose. Employing a unique partial O2 pressure (pO2) control strategy to reliably adjust the oxygen tension to values below 0.5%, we have used bioreactor cultures to investigate the metabolic rationale for this effect. A metabolic profile of the central carbon metabolism of these cultures was obtained by determination of key enzyme activities under microaerophilic as well as aerobic and anaerobic phototrophic conditions. Under aerobic conditions succinate and fructose were consumed simultaneously, whereas oxygen-limiting conditions provoked the preferential breakdown of fructose. Fructose was utilized via the Embden-Meyerhof-Parnas pathway. High levels of pyrophosphate-dependent phosphofructokinase activity were found to be specific for oxygen-limited cultures. No glucose-6-phosphate dehydrogenase activity was detected under any conditions. We demonstrate that NADPH is supplied mainly by the pyridine-nucleotide transhydrogenase under oxygen-limiting conditions. The tricarboxylic acid cycle enzymes are present at significant levels during microaerophilic growth, albeit at lower levels than those seen under fully aerobic growth conditions. Levels of the reductive tricarboxylic acid cycle marker enzyme fumarate reductase were also high under microaerophilic conditions. We propose a model by which the primary “switching” of oxidative and reductive metabolism is performed at the level of the tricarboxylic acid cycle and suggest how this might affect redox signaling and gene expression in R. rubrum. PMID:14602616

  14. The effect of zinc oxide nanoparticles deposition for friction reduction on orthodontic wires

    PubMed Central

    Kachoei, Mojghan; Eskandarinejad, Faranak; Divband, Baharak; Khatamian, Masumeh

    2013-01-01

    Background: In the sliding technique, the reduced frictional forces are associated with rapid tooth movements and better control of the anchorage. Recently, wire coating with different nanoparticles has been proposed to decrease frictional forces. This in vitro study was carried out to coat stainless steel (SS) wires with zinc oxide (ZnO) nanoparticles in order to determine the effect of this coating on friction between wires and orthodontic brackets. Materials and Methods: Eighty 0.016 inch and 0.019 inch × 0.025 inch SS wires with and without ZnO nanoparticles were used in 80 orthodontic brackets (0.018 and 0.022 systems). The coated wires were analyzed by SEM and X-Ray diffraction (XRD) observations. Kinetic friction between the wires and orthodontic brackets were calculated using a universal testing machine. Frictional forces were statistically analyzed using three-way ANOVA, one-way ANOVA, Student's t-test and Tukey multiple comparison tests. Results: Coating with ZnO nanoparticles significantly influenced frictional force values (P < 0.0001). In 0.019 inch × 0.025 inch wires, the frictional forces were 1.6912 ± 0.18868 and 3.4485 ± 0.32389 N in the coated and uncoated wires respectively, (51% reductions). In the 0.016 inch wires, the friction values were estimated to be 1.5668 ± 0.10703 and 2.56 ± 0.34008 N in the coated and uncoated conditions, respectively, (39% reductions). Conclusion: Due to the positive effects of ZnO nanoparticle coating on decreasing frictional forces, these nanoparticles might offer a novel opportunity to significantly reduce friction during tooth movement. PMID:24130586

  15. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, J.A.

    1997-12-02

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  16. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, James A. (Star City, WV)

    1997-01-01

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  17. Potential Impacts of two SO2 oxidation pathways on regional sulfate concentrations: acqueous-hase oxidation by NO2 and gas-phase oxidation by Stabilized Criegee Intermediates

    EPA Science Inventory

    We examine the potential impacts of two additional sulfate production pathways using the Community Multiscale Air Quality modeling system. First we evaluate the impact of the aqueous-phase oxidation of S(IV) by nitrogen dioxide using two published rate constants, differing by 1-2...

  18. Endoglin potentiates nitric oxide synthesis to enhance definitive hematopoiesis

    PubMed Central

    Nasrallah, Rabab; Knezevic, Kathy; Thai, Thuan; Thomas, Shane R.; Göttgens, Berthold; Lacaud, Georges; Kouskoff, Valerie; Pimanda, John E.

    2015-01-01

    ABSTRACT During embryonic development, hematopoietic cells develop by a process of endothelial-to hematopoietic transition of a specialized population of endothelial cells. These hemogenic endothelium (HE) cells in turn develop from a primitive population of FLK1+ mesodermal cells. Endoglin (ENG) is an accessory TGF-? receptor that is enriched on the surface of endothelial and hematopoietic stem cells and is also required for the normal development of hemogenic precursors. However, the functional role of ENG during the transition of FLK1+ mesoderm to hematopoietic cells is ill defined. To address this we used a murine embryonic stem cell model that has been shown to mirror the temporal emergence of these cells in the embryo. We noted that FLK1+ mesodermal cells expressing ENG generated fewer blast colony-forming cells but had increased hemogenic potential when compared with ENG non-expressing cells. TIE2+/CD117+ HE cells expressing ENG also showed increased hemogenic potential compared with non-expressing cells. To evaluate whether high ENG expression accelerates hematopoiesis, we generated an inducible ENG expressing ES cell line and forced expression in FLK1+ mesodermal or TIE2+/CD117+ HE cells. High ENG expression at both stages accelerated the emergence of CD45+ definitive hematopoietic cells. High ENG expression was associated with increased pSMAD2/eNOS expression and NO synthesis in hemogenic precursors. Inhibition of eNOS blunted the ENG induced increase in definitive hematopoiesis. Taken together, these data show that ENG potentiates the emergence of definitive hematopoietic cells by modulating TGF-?/pSMAD2 signalling and increasing eNOS/NO synthesis. PMID:25979706

  19. Structural Origin of the Activity in Mn3 O4 -Graphene Oxide Hybrid Electrocatalysts for the Oxygen Reduction Reaction.

    PubMed

    Wu, Kuang-Hsu; Zeng, Qingcong; Zhang, Bingsen; Leng, Xue; Su, Dang-Sheng; Gentle, Ian R; Wang, Da-Wei

    2015-10-01

    Non-precious metal oxide/carbon hybrid electrocatalysts are of increasing importance for the oxygen reduction reaction (ORR). A synergistic effect is commonly used to explain the superior ORR activity exerted by metal oxide/nanocarbon hybrids, and this effect is attributed to covalently coupled interfaces between the two materials. However, the origin of the high activity, the structure, and the electrocatalytic nature of the interface remain unclear. By combining X-ray photoelectron spectroscopy with synchrotron far-infrared spectroscopy, we resolved the interface structure between spinel manganese oxide nanocrystals and graphene oxide nanoribbons, and the role of this interface in the promoted ORR. Moreover, we demonstrated the excellent ORR activity by a functional synergism of the hybrid constituents through a series of comparative electrochemical experiments. PMID:26448527

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

    USGS Publications Warehouse

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

    2013-01-01

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

  1. Energy status and oxidation reduction status in rat liver at high altitude /3.8 km/

    NASA Technical Reports Server (NTRS)

    Reed, R. D.; Pace, N.

    1980-01-01

    Adult male rats were exposed to 3.8-km altitude for intervals ranging from 1 h-60 d. Liver samples were taken under light ether anesthesia and were examined by enzymatic analyses. Within 1-6 h of hypoxic exposure, ATP levels decreased while ADP and AMP levels increased, producing a fall in calculated ATP/ADP and adenylate charge ratios. Concurrently, lactate/pyruvate and alpha-glycerophosphate/dihydroxyacetone phosphate ratios increased markedly. Direct measurements of cellular pyridine nucleotides indicated increased NADH/NAD and NADPH/NADP ratios. Levels of total adenosine phosphates and pyridine nucleotides decreased in a significant accompanying response. Many metabolite levels and calculated ratios returned to near-normal values within 1 week of exposure, indicating secondary intracellular adjustments to hypoxic stress; however, persistence of that stress is reflected in lactate concentrations and both substrate redox ratios. Results support and explore concepts that increased oxidation-reduction status and decreased energy status are primary events during hypoxia.

  2. Electrochemical deposition of silver on manganese dioxide coated reduced graphene oxide for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lee, Kyungmi; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-08-01

    We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.

  3. Reduction in lipid oxidation by incorporation of encapsulated sodium tripolyphosphate in ground turkey.

    PubMed

    Sickler, Marsha L; Claus, James R; Marriott, Norman G; Eigel, William N; Wang, Hengjian

    2013-10-01

    Ground turkey, with 1% NaCl, was incorporated with no sodium tripolyphosphate (control, nSTP), unencapsulated STP (uSTP; 0.3% or 0.5%), encapsulated STP (eSTP; 0.3% or 0.5% active, phosphate basis), or a blend (0.3% uSTP plus 0.2% eSTP). Encapsulate (hydrogenated vegetable oil) was designed to melt at 74°C. Treatments were stored (4, 24h at 3°C) before being cooked to two different endpoints (EPT; 74, 79°C) followed by post-cooked storage (0, 5, 10days). An improvement of 77% (0.3% eSTP) and 80% (0.5% eSTP) in the reduction of TBARS was found in comparison to corresponding uSTP. The blend produced a 62% improvement compared to uSTP (0.5%) while maintaining cook yield. CIE a* values were highest at both EPT and post-cooked storage times beyond 0 day for eSTP. Meat manufacturing procedures that entail a delayed thermal processing step will benefit by an improvement in lipid oxidation control through the use of encapsulated phosphates. PMID:23747632

  4. Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

    NASA Astrophysics Data System (ADS)

    Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

    2015-03-01

    Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

  5. Control of the Reduction/Oxidation State of the High Level Waste Form in the Defense Waste Processing Facility at the Savannah River Site - 12451

    SciTech Connect

    Bricker, Jonathan M.; Fellinger, Terri L.; Staub, Aaron V.; Smith, Michael E.; Iaukea, John F.

    2012-07-01

    The Defense Waste Processing Facility at the Savannah River Site treats and immobilizes High Level Waste into a durable borosilicate glass for safe, permanent storage. Among the parameters important to the overall process is the reduction/oxidation state of the glass. Control strategies for the reduction/oxidation state of the glass have been developed and evolved over the last 20 years to provide a current strategy which is both accurate and robust. A description of the methodologies implemented to control, evaluate, and validate the reduction/oxidation state of the glass is discussed along with the impact of future facility changes (made to pursue a more aggressive program to empty High Level Waste tanks at the Savannah River Site) on the reduction/oxidation state of glass. The reduction/oxidation state of the glass is an important parameter to the operation of the Defense Waste Processing Facility. Control, evaluation, and validation of the reduction/oxidation state of the glass is of particular importance for melter operation. Melter feed which is too oxidizing can negatively impact production, while feed which is too reducing can result in catastrophic failure of the melter. Control strategies for the reduction/oxidation state of the glass have been developed and evolved over the last 20 years to provide a current strategy which is both accurate and robust. (authors)

  6. Enhanced Cr(VI) reduction and As(III) oxidation in ice phase: important role of dissolved organic matter from biochar.

    PubMed

    Dong, Xiaoling; Ma, Lena Q; Gress, Julia; Harris, Willie; Li, Yuncong

    2014-02-28

    This study evaluated the impact of DOM from two biochars (sugar beet tailing and Brazilian pepper) on Cr(VI) reduction and As(III) oxidation in both ice and aqueous phases with a soil DOM as control. Increasing DOM concentration from 3 to 300mgCL(-1) enhanced Cr(VI) reduction from 20% to 100% and As(III) oxidation from 6.2% to 25%; however, Cr(VI) reduction decreased from 80-86% to negligible while As(III) oxidation increased from negligible to 18-19% with increasing pH from 2 to 10. Electron spin resonance study suggested semiquinone radicals in DOM were involved in As(III) oxidation while Fourier transform infrared analysis suggested that carboxylic groups in DOM participated in both Cr(VI) reduction and As(III) oxidation. During Cr(VI) reduction, part of DOM (?10%) was oxidized to CO2. The enhanced conversion of Cr(VI) and As(III) in the ice phase was due to the freeze concentration effect with elevated concentrations of electron donors and electron acceptors in the grain boundary. Though DOM enhanced both Cr(VI) reduction and As(III)oxidation, Cr(VI) reduction coupled with As(III) oxidation occurred in absence of DOM. The role of DOM, Cr(VI) and/or As(III) in Cr and As transformation may provide new insights into their speciation and toxicity in cold regions. PMID:24418493

  7. Diversity-Oriented Synthesis Probe Targets Plasmodium falciparum Cytochrome b Ubiquinone Reduction Site and Synergizes With Oxidation Site Inhibitors

    PubMed Central

    Lukens, Amanda K.; Heidebrecht, Richard W.; Mulrooney, Carol; Beaudoin, Jennifer A.; Comer, Eamon; Duvall, Jeremy R.; Fitzgerald, Mark E.; Masi, Daniela; Galinsky, Kevin; Scherer, Christina A.; Palmer, Michelle; Munoz, Benito; Foley, Michael; Schreiber, Stuart L.; Wiegand, Roger C.; Wirth, Dyann F.

    2015-01-01

    Background.?The emergence and spread of drug resistance to current antimalarial therapies remains a pressing concern, escalating the need for compounds that demonstrate novel modes of action. Diversity-Oriented Synthesis (DOS) libraries bridge the gap between conventional small molecule and natural product libraries, allowing the interrogation of more diverse chemical space in efforts to identify probes of novel parasite pathways. Methods.?We screened and optimized a probe from a DOS library using whole-cell phenotypic assays. Resistance selection and whole-genome sequencing approaches were employed to identify the cellular target of the compounds. Results.?We identified a novel macrocyclic inhibitor of Plasmodium falciparum with nanomolar potency and identified the reduction site of cytochrome b as its cellular target. Combination experiments with reduction and oxidation site inhibitors showed synergistic inhibition of the parasite. Conclusions.?The cytochrome b oxidation center is a validated antimalarial target. We show that the reduction site of cytochrome b is also a druggable target. Our results demonstrating a synergistic relationship between oxidation and reduction site inhibitors suggests a future strategy for new combination therapies in the treatment of malaria. PMID:25336726

  8. Vibrational Stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments.

    PubMed

    Mani, Tomoyasu; Grills, David C; Miller, John R

    2015-01-28

    A recently developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ?(C?N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion pairing. This new method has the potential to probe the geometry of ion pairing and allows the reduction potentials of molecules to be determined in the absence of electrolyte in an environment of low dielectric constant. PMID:25554821

  9. Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

    SciTech Connect

    Mani, Tomoyasu; Grills, David C.; Miller, John R.

    2015-01-02

    A recently-developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ?(C?N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion-pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion-pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion-pairing. As a result, this new method has the potential to probe the geometry of ion-pairing and allows the reduction potentials of molecules to be determined in the absence of electrolyte in an environment of low dielectric constant.

  10. Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

    DOE PAGESBeta

    Mani, Tomoyasu; Grills, David C.; Miller, John R.

    2015-01-02

    A recently-developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ?(C?N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion-pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion-pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion-pairing. As a result, this new method has the potential to probe the geometry of ion-pairing and allows the reduction potentials of moleculesmore »to be determined in the absence of electrolyte in an environment of low dielectric constant.« less

  11. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    PubMed Central

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells. PMID:24448069

  12. Electrocatalytic reduction of oxygen on modified oxide surfaces. M.S. Thesis

    NASA Technical Reports Server (NTRS)

    Chaffins, Scott A.; Srinivasan, Vakula S.; Singer, Joseph

    1988-01-01

    A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

  13. Experimental and Computational Evidence for the Reduction Mechanisms of Aromatic N-oxides by Aqueous Fe(II)-Tiron Complex.

    PubMed

    Chen, Yiling; Dong, Hao; Zhang, Huichun

    2016-01-01

    A combined experimental-theoretical approach was taken to elucidate the reduction mechanisms of five representative aromatic N-oxides (ANOs) by Fe(II)-tiron complex and to identify the rate-limiting step. Based on the possible types of complexes formed with the reductant, three groups of ANOs were studied: type I refers to those forming 5-membered ring complexes through the N and O atoms on the side chain; type II refers to those forming 6-membered ring complexes through the N-oxide O atom and the O atom on the side chain; and type III refers to complexation through the N-oxide O atom only. Density functional theory calculations suggested that the elementary reactions, including protonation, N-O bond cleavage, and the second electron transfer processes, are barrierless, indicating that the first electron transfer is rate-limiting. Consistent with the theoretical results, the experimental solvent isotope effect, KIEH, for the reduction of quinoline N-oxide (a type III ANO) was obtained to be 1.072 ± 0.025, suggesting protonation was not involved in the rate-limiting step. The measured nitrogen kinetic isotope effect, KIEN, for the reduction of pyridine N-oxide (a type III ANO) (1.022 ± 0.006) is in good agreement with the calculated KIEN for its first electron transfer (1.011-1.028), confirming that the first electron transfer is rate-limiting. Electrochemical cell experiments demonstrated that the electron transfer process can be facilitated significantly by type I complexation with FeL2(6-) (1:2 Fe(II)-tiron complex), to some extent by type II complexation with free Fe(II), but not by weak type III complexation. PMID:26636617

  14. Smoking and the potential for reduction of inequalities in mortality in Europe.

    PubMed

    Kulik, Margarete C; Hoffmann, Rasmus; Judge, Ken; Looman, Caspar; Menvielle, Gwenn; Kulhánová, Ivana; Toch, Marlen; Ostergren, Olof; Martikainen, Pekka; Borrell, Carme; Rodríguez-Sanz, Maica; Bopp, Matthias; Leinsalu, Mall; Jasilionis, Domantas; Eikemo, Terje A; Mackenbach, Johan P

    2013-12-01

    Socioeconomic inequalities in health and mortality remain a widely recognized problem. Countries with smaller inequalities in smoking have smaller inequalities in mortality, and smoking plays an important part in the explanation of inequalities in some countries. We identify the potential for reducing inequalities in all-cause and smoking-related mortality in 19 European populations, by applying different scenarios of smoking exposure. Smoking prevalence information and mortality data come from 19 European populations. Prevalence rates are mostly taken from National Health Surveys conducted around the year 2000. Mortality rates are based on country-specific longitudinal or cross-sectional datasets. Relative risks come from the Cancer Prevention Study II. Besides all-cause mortality we analyze several smoking-related cancers and chronic obstructive pulmonary disease/asthma. We use a newly-developed tool to quantify the changes in population health potentially resulting from modifying the population distribution of exposure to smoking. This tool is based on the epidemiological measure of the population attributable fraction, and estimates the impact of scenario-based distributions of smoking on educational inequalities in mortality. The potential reduction of relative inequality in all-cause mortality between those with high and low education amounts up to 26 % for men and 32 % for women. More than half of the relative inequality may be reduced for some causes of death, often in countries of Northern Europe and in Britain. Patterns of potential reduction in inequality differ by country or region and sex, suggesting that the priority given to smoking as an entry-point for tackling health inequalities should differ between countries. PMID:24242935

  15. Biological reduction of uranium coupled with oxidation of ammonium by Acidimicrobiaceae bacterium A6 under iron reducing conditions.

    PubMed

    Gilson, Emily R; Huang, Shan; Jaffé, Peter R

    2015-11-01

    This study investigated the possibility of links between the biological immobilization of uranium (U) and ammonium oxidation under iron (Fe) reducing conditions. The recently-identified Acidimicrobiaceae bacterium A6 (ATCC, PTA-122488) derives energy from ammonium oxidation coupled with Fe reduction. This bacterium has been found in various soil and wetland environments, including U-contaminated wetland sediments. Incubations of Acidimicrobiaceae bacteria A6 with nontronite, an Fe(III)-rich clay, and approximately 10 µM U indicate that these bacteria can use U(VI) in addition to Fe(III) as an electron acceptor in the presence of ammonium. Measurements of Fe(II) production and ammonium oxidation support this interpretation. Concentrations of approximately 100 µM U were found to entirely inhibit Acidimicrobiaceae bacteria A6 activity. These results suggest that natural sites of active ammonium oxidation under Fe reducing conditions by Acidimicrobiaceae bacteria A6 could be hotspots of U immobilization by bioreduction. This is the first report of biological U reduction that is not coupled to carbon oxidation. PMID:26525893

  16. The physical chemistry of nucleation of sub-micrometer non-oxide ceramic powders via sub-oxide vapor-phase reduction reaction

    SciTech Connect

    Jha, A.

    1996-10-01

    Fine ceramic powders (< 500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapor-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapor species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.

  17. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    SciTech Connect

    Sato, Soshi Honjo, Hiroaki; Niwa, Masaaki; Ikeda, Shoji; Ohno, Hideo; Endoh, Tetsuo

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400?°C for 1?h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1?nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

  18. Studies on a Novel Actinobacteria Species Capable of Oxidizing Ammonium under Iron Reduction Conditions

    NASA Astrophysics Data System (ADS)

    Huanh, Shan; Ruiz-Urigüen, Melany; Jaffe, Peter R.

    2014-05-01

    Ammonium (NH4+) oxidation coupled to iron reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) was noted in a forested riparian wetland in New Jersey (1,2), and in tropical rainforest soils (3), and was coined Feammox (4). Through a 180-days anaerobic incubation of soil samples collected at the New Jersey site, and using 16S rDNA PCR-DGGE, 454-pyosequecing, and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, belonging to the phylum Actinobacteria, is responsible for this Feammox process, described previously (1,2). We have enriched these Feammox bacteria in a high efficiency Feammox membrane reactor (with 85% NH4+removal per 48h), and isolated the pure Acidimicrobiaceae bacterium A6 strain 5, in an autotrophic medium. To determine if the Feammox bacteria found in this study are common, at least at the regional scale, we analyzed a series of local wetland-, upland-, as well as storm-water detention pond-sediments. Through anaerobic incubations and molecular biology analysis, the Feammox reaction and Acidimicrobiaceae bacterium A6 were found in three of twenty soil samples collected, indicating that the Feammox pathway might be widespread in selected soil environments. Results show that soil pH and Fe(III) content are key environmental factors controlling the distributions of Feammox bacteria, which require acidic conditions and the presence of iron oxides. Results from incubation experiments conducted at different temperatures have shown that, in contrast to another anaerobic ammonium oxidation pathways (e.g., anammox), the optimal temperature of the Feammox process is ~ 20° and that the organisms are still active when the temperature is around 10°. An incubation experiment amended with acetylene gas (C2H2) as a selected inhibitor showed that in the Feammox reaction, Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+is the electron donor, which is oxidized to NO2-. After this process, NO2- is converted to nitrogen gas (N2) via conventional denitrification and/or anammox. Based on the results obtained so far, we conclude that Feammox may be an important process for nitrogen loss in iron rich, acidic soil environments under oxygen-limited conditions. Our results from operating a membrane reactor with a high Acidimicrobiaceae bacterium A6 content (~ 50%) indicate that it might be possible to develop a novel anaerobic NH4+ removal technology from wastewater based on the Feammox process, which might be more robust at low temperatures than Anammox-based processes. References 1. Clement J.C., Shrestha J., Ehrenfeld J.G., Jaffé P.R., 2005. Soil Biol Biochem 37:2323-2328. 2. Shrestha J., Rich J., Ehrenfeld J., Jaffé P.R., 2009. Soil Sci. 174:156-164. 3. Sawayama S., 2006. J Biosci Bioeng 101:70-72. 4. Yang WH, Weber KA, Silver WL, 2012. Nat Geosc 5: 538-541. 5. Huang, S., and P.R. Jaffe, 2013. Mineralogical Magazine, 77(5): 1339.

  19. Large area orientation films based on graphene oxide self-assembly and low-temperature thermal reduction

    NASA Astrophysics Data System (ADS)

    Niu, Yongan; Zhao, Jiupeng; Zhang, Xin; Wang, Xianjie; Wu, Jie; Li, Yang; Li, Yao

    2012-10-01

    Graphene oxide (GO) and reduced graphene oxide (RGO) have many outstanding physical and mechanical properties. Uniform and thickness controllable RGO films with large area were prepared by evaporation-induced self-assembly at a liquid/air interface on glass substrates in combination with low temperature thermal reduction at 200 °C. This process has the advantage of good compatibility with flexible and non-flexible substrates. The films are of centimeter scale and their thickness can be controlled. The structural evolution was characterized. The obtained thermal RGO films exhibit excellent optical properties, a high elastic modulus of 76.18 GPa, and a hardness of 6.89 GPa.

  20. Metagenome reveals potential microbial degradation of hydrocarbon coupled with sulfate reduction in an oil-immersed chimney from Guaymas Basin

    PubMed Central

    He, Ying; Xiao, Xiang; Wang, Fengping

    2013-01-01

    Deep-sea hydrothermal vent chimneys contain a high diversity of microorganisms, yet the metabolic activity and the ecological functions of the microbial communities remain largely unexplored. In this study, a metagenomic approach was applied to characterize the metabolic potential in a Guaymas hydrothermal vent chimney and to conduct comparative genomic analysis among a variety of environments with sequenced metagenomes. Complete clustering of functional gene categories with a comparative metagenomic approach showed that this Guaymas chimney metagenome was clustered most closely with a chimney metagenome from Juan de Fuca. All chimney samples were enriched with genes involved in recombination and repair, chemotaxis and flagellar assembly, highlighting their roles in coping with the fluctuating extreme deep-sea environments. A high proportion of transposases was observed in all the metagenomes from deep-sea chimneys, supporting the previous hypothesis that horizontal gene transfer may be common in the deep-sea vent chimney biosphere. In the Guaymas chimney metagenome, thermophilic sulfate reducing microorganisms including bacteria and archaea were found predominant, and genes coding for the degradation of refractory organic compounds such as cellulose, lipid, pullullan, as well as a few hydrocarbons including toluene, ethylbenzene and o-xylene were identified. Therefore, this oil-immersed chimney supported a thermophilic microbial community capable of oxidizing a range of hydrocarbons that served as electron donors for sulphate reduction under anaerobic conditions. PMID:23785357

  1. Influence of reduction conditions on electrical properties of NiO-zirconia composites for solid oxide fuel cell electrode

    NASA Astrophysics Data System (ADS)

    Orui, Himeko; Nozawa, Kazuhiko; Arai, Hajime; Kanno, Ryoji

    2015-08-01

    The electrical properties of nickel-zirconia cermets as the anode material for solid oxide fuel cells (SOFCs) were studied for Sc2O3-Al2O3-stabilized ZrO2 (SASZ), together with conventional Y2O3-stabilized ZrO2 (YSZ). The reduction behavior of the cermets in terms of achieving better electrical conductivity was examined under constant temperature ramp rate (CTR) and constant temperature (CT) conditions. The reduction process and electrical conduction thus obtained were affected by the NiO particle size and porosity, and the zirconia composition of the starting NiO-zirconia composite material. All the NiO-zirconia anodes examined in this study exhibited high conductivity after reduction at a CT of 800 °C. The CTR condition resulted in lower electrical conductivity for the Ni-zirconia cermet. In particular, NiO-SASZ using coarse NiO powder exhibited only ionic conduction with a low electronic contribution, which was due to the absence of nickel-nickel percolation. Thermogravimetric analysis of the NiO reduction indicated that NiO-SASZ and NiO-YSZ had different reduction mechanism which might correspond to the interaction between NiO and zirconia and the long-term stability of these cermets. A kinetic analysis of the NiO reduction process revealed that fast and constant nucleation during the initial stage of reduction is important for the construction of nickel-nickel connections in the cermets.

  2. Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

    NASA Astrophysics Data System (ADS)

    Miara, Lincoln James

    Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The unknown rate constants (kad, k des, k1, k1¯ ), and parameters (Ds, Q°, n) arising from the governing equations are estimated from a combination of experiments, mathematical analysis, and numerical data analysis. In the second system, dense patterned films of cathode with composition: La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF-6428) were fabricated on Ga-doped CeO2 coated YSZ substrates. These samples were analyzed by EIS over a temperature and pO 2 range of 600--800 °C and 10-3--1.00 atm, respectively. To understand the EIS results, a 2-dimensional model was developed which accounted for surface oxygen exchange, and both surface and bulk transport of oxygen to the electrolyte interface. The results were obtained by numerically solving a stationary partial differential equation describing the oxygen vacancy distribution in the cathode. From these results, the model impedance was derived and then fitted to the experimental EIS results. From the fitting results the contributions to the impedance from each of the processes were estimated. Also, the surface exchange rate was estimated over the experimental operating conditions. Finally, the results suggest that the surface diffusion occurred by an interstitial type mechanism in this material. The cathode surface is intimately involved in most of the oxygen reduction processes; however, the surface structure and chemistry is typically treated as an extension of the bulk without consideration of the actual surface properties. Recent evidence suggests that significant changes occur to the surface during operation which in turn leads to changes in electrochemical performance. To investigate these phenomena, well-oriented thin films (250 nm in thickness) of Sr-doped lanthanum manginite (LSM) films were grown on single crystals of YSZ (111). Films which were cathodically biased with a -1 V applied dc potential were compared to control samples. The cathodic bias results in both an enhancement in electrochemical performance and a change in surface chemistry. The changes in electrochemical performance were monitored by ES, while the s

  3. Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

    NASA Astrophysics Data System (ADS)

    Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

    2014-06-01

    Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ?74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (?5 vol.%), NWA 766 (<1 vol.%), NWA 3109 (<1 vol.%) and HaH 064 (<1 vol.%) as subhedral to anhedral grains comparable in size (?30 ?m to 1 mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe# = 0.55-0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine-chromite equilibration temperatures of ?1040-1050 °C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ?1200 to 1300 °C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ?0.4 ? 0.28); (2) Outer zones showing further reduction of FeO (fe# ?0.28 ? 0.15) and containing abundant laths of eskolaite-corundum (Cr2O3-Al2O3); (3) Outermost zones showing extreme reduction of both FeO (fe# <0.15) and Cr2O3 (Cr# as low as 0.2). The grains are surrounded by rims of Si-Al-rich glass, graphite, Fe, Cr-carbides ([Fe,Cr]3C and [Fe,Cr]7C3), Cr-rich sulfides (daubréelite and brezinaite) and Cr-rich symplectic bands on adjacent silicates. Chromite is inferred to have been reduced by graphite, forming eskolaite-corundum and carbides as byproducts, during impact excavation. This event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to <700 °C) at 1-20 °C/h. The kinetics of reduction of chromite is consistent with this scenario. The reduction was facilitated by silicate melt surrounding the chromites, which was partly generated by shock-melting of pyroxenes. Symplectic bands, consisting of fine-scale intergrowths of Ca-pyroxene, chromite and glass, formed by reaction between the Cr-enriched melt and adjacent silicates. Early chromite also occurs in a melt inclusion in olivine in HaH 064 and in a metallic spherule in olivine in LAP 02382. LAP 03587 and CMS 04048 contain ??m-sized chromite + pyroxene symplectic exsolutions in olivine, indicating high Cr valence in the primary olivine. EET 96328 contains a round grain of chromite that could be a late-crystallizing phase. Tiny chromite grains in melt inclusions in EET 96328 formed in late, closed-system reactions. For 7 of the 8 ureilites we conclude that the relatively oxidizing conditions evidenced by the presence of primary or early chromite pertain to the period of high-T igneous processing. The observation that such conditions are recorded almost exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

  4. Reductive Reactivity of Iron(III) Oxides in the East China Sea Sediments: Characterization by Selective Extraction and Kinetic Dissolution

    PubMed Central

    Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

    2013-01-01

    Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k? (rate constant) and ? (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m0, k? and ?, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases. PMID:24260377

  5. Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

    SciTech Connect

    Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

    2012-11-13

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

  6. Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

    DOEpatents

    Adzic, Radoslav (East Setauket, NY); Zhang, Junliang (Stony Brook, NY); Vukmirovic, Miomir (Port Jefferson Station, NY)

    2011-11-22

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

  7. Investigation into the oxidative potential generated by the formation of particulate matter from incense combustion.

    PubMed

    Chuang, Hsiao-Chi; BéruBé, Kelly; Lung, Shih-Chun C; Bai, Kuan-Jen; Jones, Tim

    2013-01-15

    The formation of aerosols during combustion plays an important role in allowing released products to interreact, leading to an increase in particulate matter oxidative potential. This study investigated the physicochemistry of incense combustion-derived pollutants, which were emitted into the ambient air as solid and gas phases, followed by the determination of their oxidative potential. Upon combustion of a joss stick, approximately 60% of the mass of incense raw ingredients was released into the ambient air as combustion products including 349.51 mg/g PM(10), 145.48 mg/g CO and 0.16 mg/g NOx. Furthermore, incense combustion produced significant number of primary particles (<50 nm) at 0.99×10(5) 1/h. The NOx generated during incense combustion was able to react with CaCO(3) to produce the final product of Ca(NO(3))(2) in the ambient air. Moreover, coagulation could be a vital process for the growth of primary incense combustion particles through the intermixing with volatile organics. The incense particle's reactions with other combustion-derived products could be responsible for their significant oxidative capacity of 33.1-43.4% oxidative DNA damage. This study demonstrated that the oxidative potential of incense particles appeared to be related to the process of particle formation, and also provided novel data for the respiratory exposure assessment. PMID:23246950

  8. Potential for in situ chemical oxidation of acid extractable organics in oil sands process affected groundwater.

    PubMed

    Sohrabi, V; Ross, M S; Martin, J W; Barker, J F

    2013-11-01

    The process of bitumen extraction from oil sands in Alberta, Canada leads to an accumulation of toxic acid-extractable organics (AEOs) in oil sands process water (OSPW). Infiltration of OSPW from tailings ponds and from their retaining sand dykes and subsequent transport towards surface water has occurred. Given the apparent lack of significant natural attenuation of AEOs in groundwater, remediation may be required. This laboratory study evaluates the potential use of unactivated persulfate and permanganate as in situ oxidation agents for remediation of AEOs in groundwater. Naphthenic acids (NAs; CnH2n+zO2), which are a component of the acutely toxic AEOs, were degraded by both oxidants in OSPW samples. Permanganate oxidation yielded some residual dissolved organic carbon (DOC) whereas persulfate mineralized the AEO compounds with less residual DOC. Acid-extractable organics from oxidized OSPW had essentially no Microtox toxicity. PMID:24054134

  9. Oxidation Potentials of Functionalized Sulfone Solvents for High-Voltage Li-Ion Batteries: A Computational Study

    SciTech Connect

    Shao, Nan; Sun, Xiao-Guang; Dai, Sheng; Jiang, Deen

    2012-01-01

    New electrolytes with large electrochemical windows are needed to meet the challenge for high-voltage Li-ion batteries. Sulfone as an electrolyte solvent boasts of high oxidation potentials. Here we examine the effect of multiple functionalization on sulfone's oxidation potential. We compute oxidation potentials for a series of sulfone-based molecules functionalized with fluorine, cyano, ester, and carbonate groups by using a quantum chemistry method within a continuum solvation model. We find that multifunctionalization is a key to achieving high oxidation potentials. This can be realized through either a fluorether group on a sulfone molecule or sulfonyl fluoride with a cyano or ester group.

  10. Benthic ammonia oxidizers differ in community structure and biogeochemical potential across a riverine delta.

    PubMed

    Damashek, Julian; Smith, Jason M; Mosier, Annika C; Francis, Christopher A

    2014-01-01

    Nitrogen pollution in coastal zones is a widespread issue, particularly in ecosystems with urban or agricultural watersheds. California's Sacramento-San Joaquin Delta, at the landward reaches of San Francisco Bay, is highly impacted by both agricultural runoff and sewage effluent, leading to chronically high nutrient loadings. In particular, the extensive discharge of ammonium into the Sacramento River has altered this ecosystem by vastly increasing ammonium concentrations and thus changing the stoichiometry of inorganic nitrogen stocks, with potential effects throughout the food web. This debate surrounding ammonium inputs highlights the importance of understanding the rates of, and controls on, nitrogen (N) cycling processes across the delta. To date, however, there has been little research examining N biogeochemistry or N-cycling microbial communities in this system. We report the first data on benthic ammonia-oxidizing microbial communities and potential nitrification rates for the Sacramento-San Joaquin Delta, focusing on the functional gene amoA (which codes for the ?-subunit of ammonia monooxygenase). There were stark regional differences in ammonia-oxidizing communities, with ammonia-oxidizing bacteria (AOB) outnumbering ammonia-oxidizing archaea (AOA) only in the ammonium-rich Sacramento River. High potential nitrification rates in the Sacramento River suggested these communities may be capable of oxidizing significant amounts of ammonium, compared to the San Joaquin River and the upper reaches of San Francisco Bay. Gene diversity also showed regional patterns, as well as phylogenetically unique ammonia oxidizers in the Sacramento River. The benthic ammonia oxidizers in this nutrient-rich aquatic ecosystem may be important players in its overall nutrient cycling, and their community structure and biogeochemical function appear related to nutrient loadings. Unraveling the microbial ecology and biogeochemistry of N cycling pathways, including benthic nitrification, is a critical step toward understanding how such ecosystems respond to the changing environmental conditions wrought by human development and climate change. PMID:25620958

  11. Benthic ammonia oxidizers differ in community structure and biogeochemical potential across a riverine delta

    PubMed Central

    Damashek, Julian; Smith, Jason M.; Mosier, Annika C.; Francis, Christopher A.

    2015-01-01

    Nitrogen pollution in coastal zones is a widespread issue, particularly in ecosystems with urban or agricultural watersheds. California's Sacramento-San Joaquin Delta, at the landward reaches of San Francisco Bay, is highly impacted by both agricultural runoff and sewage effluent, leading to chronically high nutrient loadings. In particular, the extensive discharge of ammonium into the Sacramento River has altered this ecosystem by vastly increasing ammonium concentrations and thus changing the stoichiometry of inorganic nitrogen stocks, with potential effects throughout the food web. This debate surrounding ammonium inputs highlights the importance of understanding the rates of, and controls on, nitrogen (N) cycling processes across the delta. To date, however, there has been little research examining N biogeochemistry or N-cycling microbial communities in this system. We report the first data on benthic ammonia-oxidizing microbial communities and potential nitrification rates for the Sacramento-San Joaquin Delta, focusing on the functional gene amoA (which codes for the ?-subunit of ammonia monooxygenase). There were stark regional differences in ammonia-oxidizing communities, with ammonia-oxidizing bacteria (AOB) outnumbering ammonia-oxidizing archaea (AOA) only in the ammonium-rich Sacramento River. High potential nitrification rates in the Sacramento River suggested these communities may be capable of oxidizing significant amounts of ammonium, compared to the San Joaquin River and the upper reaches of San Francisco Bay. Gene diversity also showed regional patterns, as well as phylogenetically unique ammonia oxidizers in the Sacramento River. The benthic ammonia oxidizers in this nutrient-rich aquatic ecosystem may be important players in its overall nutrient cycling, and their community structure and biogeochemical function appear related to nutrient loadings. Unraveling the microbial ecology and biogeochemistry of N cycling pathways, including benthic nitrification, is a critical step toward understanding how such ecosystems respond to the changing environmental conditions wrought by human development and climate change. PMID:25620958

  12. The CO2 Reduction Potential of Combined Heat and Power in California's Commercial Buildings

    SciTech Connect

    Stadler, Michael; Marnay, Chris; Cardoso, Goncalo; Lipman, Tim; Megel, Olivier; Ganguly, Srirupa; Siddiqui, Afzal; Lai, Judy

    2009-11-16

    The Ernest Orlando Lawrence Berkeley National Laboratory (LBNL) is working with the California Energy Commission (CEC) to determine the potential role of commercial sector distributed generation (DG) with combined heat and power (CHP) capability deployment in greenhouse gas emissions (GHG) reductions. CHP applications at large industrial sites are well known, and a large share of their potential has already been harvested. In contrast, relatively little attention has been paid to the potential of medium-sized commercial buildings, i.e., ones with peak electric loads ranging from 100 kW to 5 MW. We examine how this sector might implement DG with CHP in cost minimizing microgrids that are able to adopt and operate various energy technologies, such as solar photovoltaics (PV), on-site thermal generation, heat exchangers, solar thermal collectors, absorption chillers, and storage systems. We apply a mixed-integer linear program (MILP) that minimizes a site's annual energy costs as its objective. Using 138 representative mid-sized commercial sites in California (CA), existing tariffs of three major electricity distribution ultilities plus a natural gas company, and performance data of available technology in 2020, we find the GHG reduction potential for this CA commercial sector segment, which represents about 35percent of total statewide commercial sector sales. Under the assumptions made, in a reference case, this segment is estimated to be capable of economically installing 1.4 GW of CHP, 35percent of the California Air Resources Board (CARB) statewide 4 GW goal for total incremental CHP deployment by 2020. However, because CARB's assumed utilization is far higherthan is found by the MILP, the adopted CHP only contributes 19percent of the CO2 target. Several sensitivity runs were completed. One applies a simple feed-in tariff similar to net metering, and another includes a generous self-generation incentive program (SGIP) subsidy for fuel cells. The feed-in tariff proves ineffective at stimulating CHP deployment, while the SGIP buy down is more powerful. The attractiveness of CHP varies widely by climate zone and service territory, but in general, hotter inland areas and San Diego are the more attractive regions because high cooling loads achieve higher equipment utilization. Additionally, large office buildings are surprisingly good hosts for CHP, so large office buildings in San Diego and hotter urban centers emerge as promising target hosts. Overall the effect on CO2 emissions is limited, never exceeding 27percent of the CARB target. Nonetheless, results suggest that the CO2 emissions abatement potential of CHP in mid-sized CA buildings is significant, and much more promising than is typically assumed.

  13. COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES

    EPA Science Inventory

    Semiempirical molecular orbital theory and density functional theory are used to compute one-electron oxidation potentials for aniline and a set of 21 mono- and di-substituted anilines in aqueous solution. Linear relationships between theoretical predictions and experiment are co...

  14. Oxidized Volcanic Materials as a Potential Explanation for Gray Hematite Regions on Mars

    NASA Technical Reports Server (NTRS)

    Minitti, M. E.; Lane, M. D.; Bishop, J. L.

    2002-01-01

    Martian-analogue basalts synthesized, then oxidized, in the laboratory exhibit gray hematite coatings on exposed glass surfaces. We explore potential connections between these hematite coatings and the coarse, gray hematite signatures seen on Mars. Additional information is contained in the original extended abstract.

  15. Influence of oxygenated organic aerosols (OOAs) on the oxidative potential of diesel and biodiesel particulate matter.

    PubMed

    Stevanovic, S; Miljevic, B; Surawski, N C; Fairfull-Smith, K E; Bottle, S E; Brown, R; Ristovski, Z D

    2013-07-16

    Generally, the magnitude of pollutant emissions from diesel engines running on biodiesel fuel is ultimately coupled to the structure of the fuel's constituent molecules. Previous studies demonstrated the relationship between the organic fraction of particulate matter (PM) and its oxidative potential. Herein, emissions from a diesel engine running on different biofuels were analyzed in more detail to explore the role that different organic fractions play in the measured oxidative potential. In this work, a more detailed chemical analysis of biofuel PM was undertaken using a compact time of flight aerosol mass spectrometer (c-ToF AMS). This enabled a better identification of the different organic fractions that contribute to the overall measured oxidative potentials. The concentration of reactive oxygen species (ROS) was measured using a profluorescent nitroxide molecular probe 9-(1,1,3,3-tetramethylisoindolin-2-yloxyl-5-ethynyl)-10-(phenylethynyl)anthracene (BPEAnit). Therefore, the oxidative potential of the PM, measured through the ROS content, although proportional to the total organic content in certain cases, shows a much higher correlation with the oxygenated organic fraction as measured by the c-ToF AMS. This highlights the importance of knowing the surface chemistry of particles for assessing their health impacts. It also sheds light onto new aspects of particulate emissions that should be taken into account when establishing relevant metrics for assessing health implications of replacing diesel with alternative fuels. PMID:23763365

  16. Fluxes of nitrous oxide and carbon dioxide over four potential biofuel crops in Central Illinois

    NASA Astrophysics Data System (ADS)

    Zeri, M.; Hickman, G. C.; Bernacchi, C.

    2009-12-01

    Nitrous oxide (N2O) and carbon dioxide (CO2) are important greenhouse gases that contribute to global climate change. Agriculture is a significant source of N2O to the atmosphere due to the use of nitrogen-based fertilizers. Fluxes of N2O and CO2 are measured using the flux-gradient technique over four different crops at the Energy Farm, a University of Illinois research facility in Urbana, Illinois. Measurements started in June of 2009 and are part of a project that aims to assess the impacts of potential biofuel crops on the carbon, water and nitrogen cycles. The species chosen are Maize (Zea mays), Miscanthus (Miscanthus x giganteus), Switchgrass (Panicum virgatum) and Prairie (a mix of several native species). The choice of species was based on their potential for the production of second-generation biofuels, i.e., fuels derived from the decomposition of the cellulosic material in the plant biomass. The use of corn residue for cellulosic biofuels might impact the carbon cycle through the reduction of soil organic content. Miscanthus is a perennial grass with great potential for biomass production. However, the total water used during the growing season and its water use efficiency might impose limits on the regions where this biofuel crop can be sustainably planted on a large scale. Switchgrass and the prairie species are less productive but might be suited for being well adapted and easy to establish. This study is the first side-by-side comparison of fluxes of N2O for these agro-ecosystems. The measurements are performed at micrometeorological towers placed at the center of 4 ha plots. The air is sampled at two heights over the vegetation and is analyzed in a tunable diode laser (TDL) installed nearby. A valve system cycles the TDL measurements trough all the intakes in the plots. The fluxes are calculated using the flux-gradient method, which requires the knowledge of the scalar vertical gradient as well as of the friction velocity (u*) and the Monin-Obukhov stability parameter L. The last two variables are provided by eddy covariance systems in each field. Preliminary results show a good agreement between CO2 fluxes derived from the flux-gradient and eddy covariance methods for daytime conditions. This agreement is a good validation of the calculations and confirms that the N2O fluxes are being correctly estimated. The two methods disagree during nighttime due to the underestimation of eddy covariance fluxes for non-turbulent conditions. The fluxes of nitrous oxide at the corn plot were stronger and responded faster to precipitation. The highest fluxes were observed during the second half of June 2009 after a series of rain events. The highest emission at this time occurred for corn, followed by Miscanthus (half of what was observed for corn). Prairie and switchgrass presented half and a quarter, respectively, of what was observed for miscanthus.

  17. Distant electric coupling between nitrate reduction and sulphide oxidation investigated by an improved nitrate microscale biosensor

    NASA Astrophysics Data System (ADS)

    Marzocchi, U.; Revsbech, N. P.; Nielsen, L. P.; Risgaard-Petersen, N.

    2012-04-01

    Bacteria are apparently able to transmit electrons to other bacteria (Summers et al. 2010) or to electrodes (Malvankar et al. 2011) by some kind of nanowires (Reguera et al. 2005, Gorbi et al. 2006). Lately it has been shown that such transfer may occur over distances of centimetres in sediments, thereby coupling sulphide oxidation in deeper layers with oxygen reduction near the surface (Nielsen 2011). The finding of these long-distance electrical connections originated from analysis of O2, H2S, and pH profiles measured with microsensors. Nitrate is thermodynamically almost as good an electron acceptor as O2, and we therefore set up an experiment to investigate whether long-distance electron transfer also happens with NO3-. Aquaria were filled with sulphidic marine sediment from Aarhus Bay that was previously used to show long-distance electron transfer to O2. The aquaria were equipped with a lid so that they could be completely filled without a gas phase. Anoxic seawater with 300 ?M NO3- was supplied at a constant rate resulting in a steady state concentration in the aquatic phase of 250 ?M NO3-. The reservoir with the nitrate-containing water was kept anoxic by bubbling it with a N2/CO2 mixture and was kept at an elevated temperature. The water was cooled on the way to the aquaria to keep the water in the aquaria undersaturated with gasses, so that bubble formation by denitrification in the sediment could be minimised. Profiles of NO3-, H2S, and pH were measured as a function of time (2 months) applying commercial sensors for H2S and pH and an improved microscale NO3- biosensor developed in our laboratory. The penetration of NO3- in the sediment was 4-5 mm after 2 months, whereas sulphide only could be detected below 8-9 mm depth. The electron acceptor and electron donor were thus separated by 4-5 mm, indicating long distance electron transfer. A pH maximum of about 8.6 pH units at the NO3- reduction zone similar to a pH maximum observed in the O2 reduction zone of electro-active sediments could be observed. This pH maximum was the strongest evidence for long-distance electron transfer in oxic sediments, but cannot be taken as proof in denitrifying sediments as conventional denitrification may also produce elevated pH. We are now searching for the NO3- reducing bacteria that may be active in long-distance electron transfer in our sediment. Gorby, Y. A., S. Yanina, et al. (2006). Electrically conductive bacterial nanowires produced by Shewanella oneidensis strain MR-1 and other microorganisms. Proceedings of the National Academy of Sciences of the United States of America 103(30): 11358-11363. Malvankar, N. S., M. Vargas, et al. (2011). Tunable metallic-like conductivity in microbial nanowire networks. Nature Nanotechnology 6(9): 573-579. Nielsen, L. P., N. Risgaard-Petersen, et al. (2010). Electric currents couple spatially separated biogeochemical processes in marine sediment. Nature 463(7284): 1071-1074. Reguera, G., K. D. McCarthy, et al. (2005). Extracellular electron transfer via microbial nanowires. Nature 435(7045): 1098-1101. Summers, Z. M., H. E. Fogarty, et al. (2010). Direct Exchange of Electrons Within Aggregates of an Evolved Syntrophic Coculture of Anaerobic Bacteria. Science 330(6009): 1413-1415.

  18. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries.

    PubMed

    Suntivich, Jin; Gasteiger, Hubert A; Yabuuchi, Naoaki; Nakanishi, Haruyuki; Goodenough, John B; Shao-Horn, Yang

    2011-07-01

    The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to ?-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the ? orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity. PMID:21697876

  19. Impacts of potential CO2-reduction policies on air quality in the United States.

    PubMed

    Trail, Marcus A; Tsimpidi, Alexandra P; Liu, Peng; Tsigaridis, Kostas; Hu, Yongtao; Rudokas, Jason R; Miller, Paul J; Nenes, Athanasios; Russell, Armistead G

    2015-04-21

    Impacts of emissions changes from four potential U.S. CO2 emission reduction policies on 2050 air quality are analyzed using the community multiscale air quality model (CMAQ). Future meteorology was downscaled from the Goddard Institute for Space Studies (GISS) ModelE General Circulation Model (GCM) to the regional scale using the Weather Research Forecasting (WRF) model. We use emissions growth factors from the EPAUS9r MARKAL model to project emissions inventories for two climate tax scenarios, a combined transportation and energy scenario, a biomass energy scenario and a reference case. Implementation of a relatively aggressive carbon tax leads to improved PM2.5 air quality compared to the reference case as incentives increase for facilities to install flue-gas desulfurization (FGD) and carbon capture and sequestration (CCS) technologies. However, less capital is available to install NOX reduction technologies, resulting in an O3 increase. A policy aimed at reducing CO2 from the transportation sector and electricity production sectors leads to reduced emissions of mobile source NOX, thus reducing O3. Over most of the U.S., this scenario leads to reduced PM2.5 concentrations. However, increased primary PM2.5 emissions associated with fuel switching in the residential and industrial sectors leads to increased organic matter (OM) and PM2.5 in some cities. PMID:25811418

  20. Amplitude reduction in visual event-related potentials as a function of sleep deprivation.

    PubMed

    Corsi-Cabrera, M; Arce, C; Del Río-Portilla, I Y; Pérez-Garci, E; Guevara, M A

    1999-03-15

    Eight adult males were subjected to 40 hours of total sleep deprivation (TSD). Reaction time in a visual task and electroncephalographam (C3) were evaluated every 2 hours. One second of EEG before the stimuli was Fourier-transformed, and 750 ms after target and nontarget stimuli were averaged and visual event-related potentials (ERP) were obtained. Factorial analysis identified time windows that showed significant amplitude reduction and longer latencies with TSD: (1) 140 to 288 ms (P180-N242-P281); (2) 288 to 413 ms and 601 to 749 ms (N382; P718) and; (3) 531 to 601 ms (N500). Effect was strongest for N382 and P718, the amplitudes of which dropped to 20% of original size. The entire waveform recovered initial amplitudes and latencies after recovery sleep except for P718 latency. Waveforms within similar time intervals have been associated with attentional gating, sensory discrimination, target selection, uncertainty and decision processes. Amplitudes of the visual ERP were inversely correlated with hours of TSD, reaction time, and absolute power of the prestimulus EEG. Present results clearly show changes in fundamental neurophysiologic mechanisms as a result of TSD, indicating variability and reduction of the alertness mechanisms and changes in thalamocortical gating affecting attention, discrimination and decision-making. PMID:10201062

  1. NASA's Vision for Potential Energy Reduction from Future Generations of Propulsion Technology

    NASA Technical Reports Server (NTRS)

    Haller, Bill

    2015-01-01

    Through a robust partnership with the aviation industry, over the past 50 years NASA programs have helped foster advances in propulsion technology that enabled substantial reductions in fuel consumption for commercial transports. Emerging global trends and continuing environmental concerns are creating challenges that will very likely transform the face of aviation over the next 20-40 years. In recognition of this development, NASA Aeronautics has established a set of Research Thrusts that will help define the future direction of the agency's research technology efforts. Two of these thrusts, Ultra-Efficient Commercial Vehicles and Transition to Low-Carbon Propulsion, serve as cornerstones for the Advanced Air Transport Technology (AATT) project. The AATT project is exploring and developing high-payoff technologies and concepts that are key to continued improvement in energy efficiency and environmental compatibility for future generations of fixed-wing, subsonic transports. The AATT project is primarily focused on the N+3 timeframe, or 3 generations from current technology levels. As should be expected, many of the propulsion system architectures technologies envisioned for N+3 vary significantly from todays engines. The use of batteries in a hybrid-electric configuration or deploying multiple fans distributed across the airframe to enable higher bypass ratios are just two examples of potential advances that could enable substantial energy reductions over current propulsion systems.

  2. Web-Based Computational Chemistry Education with CHARMMing III: Reduction Potentials of Electron Transfer Proteins

    PubMed Central

    Perrin, B. Scott; Miller, Benjamin T.; Schalk, Vinushka; Woodcock, H. Lee; Brooks, Bernard R.; Ichiye, Toshiko

    2014-01-01

    A module for fast determination of reduction potentials, E°, of redox-active proteins has been implemented in the CHARMM INterface and Graphics (CHARMMing) web portal (www.charmming.org). The free energy of reduction, which is proportional to E°, is composed of an intrinsic contribution due to the redox site and an environmental contribution due to the protein and solvent. Here, the intrinsic contribution is selected from a library of pre-calculated density functional theory values for each type of redox site and redox couple, while the environmental contribution is calculated from a crystal structure of the protein using Poisson-Boltzmann continuum electrostatics. An accompanying lesson demonstrates a calculation of E°. In this lesson, an ionizable residue in a [4Fe-4S]-protein that causes a pH-dependent E° is identified, and the E° of a mutant that would test the identification is predicted. This demonstration is valuable to both computational chemistry students and researchers interested in predicting sequence determinants of E° for mutagenesis. PMID:25058418

  3. Obese Smokers as a Potential Subpopulation of Risk in Tobacco Reduction Policy

    PubMed Central

    Rupprecht, Laura E.; Donny, Eric C.; Sved, Alan F.

    2015-01-01

    Smoking and obesity represent the largest challenges to public health. There is an established inverse relationship between body mass index (BMI) and smoking, but this relationship becomes more complicated among obese smokers. Smokers with higher BMI consume more cigarettes per day and may be more nicotine-dependent than lean smokers. Rates of obesity are lower among smokers than non-smokers, indicating that chronic exposure to tobacco smoke may prevent excess weight gain in people who would otherwise become obese. Furthermore, obese smokers may be more sensitive to the weight-suppressive and reinforcing effects of nicotine. Consequently, obese smokers may respond differently to reduction in the nicotine content of cigarettes, a tobacco control policy being considered both in the Unites States and abroad. Here, we review the interrelationship between nicotine and obesity in the context of a potential nicotine reduction policy. We discuss the implications of nicotine-induced body weight suppression in obese smokers, as well as the possibility that obesity might increase susceptibility to smoking and nicotine dependence. PMID:26339212

  4. DEMONSTRATION OF POTENTIAL FOR SELECTIVE CATALYTIC REDUCTION AND DIESEL PARTICULATE FILTERS

    SciTech Connect

    McGILL,R; KHAIR, M; SHARP, C

    2003-08-24

    This project addresses the potential for Selective Catalytic Reduction (SCR) devices (using urea as reductant) together with Diesel Particulate Filters (DPF) and low-pressure loop exhaust gas recirculation (EGR) to achieve future stringent emissions standards for heavy-duty engines powering Class 8 vehicles. Two emission control systems consisting of the three technologies (EGR, SCR, and DPF) were calibrated on a Caterpillar C-12 heavy-duty diesel engine. Results of these calibrations showed good promise in meeting the 2010 heavy-duty emission standards as set forth by the Environmental Protection Agency (EPA). These two emission control systems were developed to evaluate a series of fuels that have similar formulations except for their sulfur content. Additionally, one fuel, code-named BP15, was also evaluated. This fuel was prepared by processing straight-run distillate stocks through a commercial, single stage hydrotreater employing high activity catalyst at maximum severity. An additional goal of this program is to provide data for an on-going EPA technology review that evaluates progress toward meeting 2007/2010 emission standards. These emissions levels were to be achieved not only on the transient test cycles but in other modes of operation such as the steady-state Euro-III style emission test known as the OICA (Organisation Internationale des Compagnies d'Automobiles) or the ESC (European Stationary Cycle). Additionally, hydrocarbon and carbon monoxide emissions standards are to be met.

  5. Polypyrrole-hemin-reduce graphene oxide: rapid synthesis and enhanced electrocatalytic activity towards the reduction of hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Huang, Wenjing; Hao, Qingli; Lei, Wu; Wu, Lihua; Xia, Xifeng

    2014-12-01

    An efficient and eco-friendly microwave-assistant method is developed to synthesize a ternary composite of polypyrrole-hemin-reduced graphene oxide (PPY-He-RGO). The polymerization of the pyrrole monomer and the reduction of graphene oxide are performed simply by microwave heating without using a strong reducing or oxidizing agent in an isopropanol/H2O mixed medium. Hemin molecules are immobilized on reduced graphene oxide (RGO) sheets and can still retain high electrocatalytic activity toward the reduction of H2O2 in the final composite. The conducting RGO and polypyrrole with a well-controlled nanostructure provide a highly conductive network to the ternary composite, which can promote the electron transfer between hemin, analytes and electrodes, leading to an improved electrocatalytic activity. The PPY-He-RGO can act as a third-generation mediator and mimic enzyme for the fabrication of a hydrogen peroxide biosensor. The as-prepared PPY-He-RGO electrode exhibits a high sensitivity to H2O2 with a low detection limit of 0.13 ?m. The efficient microwave heating provides an opportunity for large-scale production of PPY-He-RGO ternary nanocomposites as a kind of mimic enzyme for biosensors.

  6. Quantification of the Potential Gross Economic Impacts of Five Methane Reduction Scenarios

    SciTech Connect

    Keyser, David; Warner, Ethan; Curley, Christina

    2015-04-23

    Methane (CH4) is a potent greenhouse gas that is released from the natural gas supply chain into the atmosphere as a result of fugitive emissions1 and venting2 . We assess five potential CH4 reduction scenarios from transmission, storage, and distribution (TS&D) using published literature on the costs and the estimated quantity of CH4 reduced. We utilize cost and methane inventory data from ICF (2014) and Warner et al. (forthcoming) as well as data from Barrett and McCulloch (2014) and the American Gas Association (AGA) (2013) to estimate that the implementation of these measures could support approximately 85,000 jobs annually from 2015 to 2019 and reduce CH4 emissions from natural gas TS&D by over 40%. Based on standard input/output analysis methodology, measures are estimated to support over $8 billion in GDP annually over the same time period and allow producers to recover approximately $912 million annually in captured gas.

  7. Potential of size reduction of flat-plate solar collectors when applying MWCNT nanofluid

    NASA Astrophysics Data System (ADS)

    Faizal, M.; Saidur, R.; Mekhilef, S.

    2013-06-01

    Flat-plate solar collector is the most popular type of collector for hot water system to replace gas or electric heater. Solar thermal energy source is clean and infinite to replace fossil fuel source that is declining and harmful to the environment. However, current solar technology is still expensive, low in efficiency and takes up a lot of space. One effective way to increase the efficiency is by applying high conductivity fluid as nanofluid. This paper analyzes the potential of size reduction of solar collector when MWCNT nanofluid is used as absorbing medium. The analysis is based on different mass flow rate, nanoparticles mass fraction, and presence of surfactant in the fluid. For the same output temperature, it can be observed that the collector's size can be reduced up to 37% of its original size when applying MWCNT nanofluid as the working fluid and thus can reduce the overall cost of the system.

  8. Characterization of Binary Ag-Cu Ion Mixtures in Zeolites: Their Reduction Products and Stability to Air Oxidation

    SciTech Connect

    Fiddy, Steven; Petranovskii, Vitalii; Ogden, Steve; Iznaga, Inocente Rodriguez

    2007-02-02

    A series of Ag+-Cu2+ binary mixtures with different Ag/Cu ratios were supported on mordenite with different Si/Al ratios and were subsequently reduced under hydrogen in the temperature range 323K - 473K. Ag and Cu K-edge X-ray Absorption Spectroscopy (XAS) was conducted on these systems in-situ to monitor the reduction species formed and the kinetics of their reduction. In-situ XANES clearly demonstrates that the formation of silver particles is severely impeded by the addition of copper and that the copper is converted from Cu(II) to Cu(I) during reduction and completely reverts back to Cu(II) during cooling. There are no indications at any stage of the formation of bimetallic Ag-Cu clusters. Interestingly, the Ag/Cu ratio appears to have no influence of the reduction kinetics and reduction products formed with only the highest Si/Al ratio (MR = 128) investigated during this study having an influence on the reduction</