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. The effect of shock on blood oxidation-reduction potential

    Microsoft Academic Search

    M. Jellinek; B. Chandel; R. Abdulla; M. J. Shapiro; A. E. Baue

    1992-01-01

    Oxidation-reduction (redox) potential measurements were made in the blood of rabbits subjected to hemorrhagic shock followed by treatment with a mild oxidizing agent (albumin). Control redox potential reading corrected for pH was ?8.8±1.3 millivolts (mV) in arterial blood (A) and ?18.0±2.0 mV in venous blood (V). This A-V difference indicated that hydrogen equivalents coming from muscle and other tissues were

  3. 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 ...

  4. 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.

  5. 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

  6. Standard test method for measurement of oxidation-reduction potential (ORP) of soil

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2009-01-01

    1.1 This test method covers a procedure and related test equipment for measuring oxidation-reduction potential (ORP) of soil samples removed from the ground. 1.2 The procedure in Section 9 is appropriate for field and laboratory measurements. 1.3 Accurate measurement of oxidation-reduction potential aids in the analysis of soil corrosivity and its impact on buried metallic structure corrosion rates. 1.4 The values stated in inch-pound units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  7. Analysis of the oxidation-reduction potentials of recombinant ferredoxin-NADP+ reductase from spinach chloroplasts.

    PubMed

    Corrado, M E; Aliverti, A; Zanetti, G; Mayhew, S G

    1996-08-01

    Midpoint oxidation-reduction potentials for the two-electron reduction of the bound FAD in spinach ferredoxin-NADP+ reductase were measured by potentiometry (Em = -342 +/- 1 mV at pH 7 and 10 degrees C). They were used with the semiquinone formation constant, obtained by spectroscopic measurement of the semiquinone concentration, to calculate values for the redox potentials of the two one-electron steps in the reduction. The redox potential for the oxidized enzyme/enzyme semiquinone couple (EOX/SQ) at pH 7 is -350 +/- 2 mV (10 degrees C) while the value for the enzyme semiquinone/enzyme hydroquinone couple (ESQ/HQ) under the same conditions is -335 +/- 1 mV. These values correspond to a semiquinone formation constant of 0.55. Measurement of the effects of pH on the potentials showed that EOX/SQ varies linearly with pH (slope -46 +/- 4 mV), while ESQ/HQ is independent of pH at high pH values, but below about pH 7.5 the potential becomes less negative with decreasing pH. indicating that there is a redox-linked protonation of the fully reduced enzyme (pKa = 7.2, 10 degrees C). The absorption spectrum of the fully reduced enzyme was found to depend on pH with the changes giving a calculated pKa of 7.5 (at 15 degrees C). The spectrum at high pH is similar to that of the anionic form of free flavin hydroquinone. The observations suggest that at physiological pH, the enzyme FAD cycles between the three redox states: oxidized, neutral semiquinone and hydroquinone anion. PMID:8774710

  8. Application of a new oxidation-reduction potential assessment method in strenuous exercise-induced oxidative stress.

    PubMed

    Stagos, Dimitrios; Goutzourelas, Nikolaos; Bar-Or, David; Ntontou, Amalia-Maria; Bella, Evangelia; Becker, Aphrodite Tousia; Statiri, Argyro; Kafantaris, Ioannis; Kouretas, Dimitrios

    2015-07-01

    Objectives The aim of the study was to test a novel method for assessing oxidative stress, the RedoxSYS™ diagnostic system, a holistic, fast, minimally invasive, and requiring small sample volume method, that measures two parameters, the static (sORP) and the capacity (cORP) oxidation-reduction potential. Methods The redox status of 14 athletes participating in a mountain marathon race was assessed. Redox status in blood obtained 1 day before the race and immediately after the race was assessed using the RedoxSYS diagnostic system as well as conventional oxidative stress markers such as glutathione levels (GSH), catalase activity (CAT), thiobarbituric acid reactive substances (TBARS), protein carbonyls (CARB), and total antioxidant activity. Results The results showed that after the race, the sORP was increased significantly by 7% indicating oxidative stress induction, while cORP was decreased by 14.6% but not significantly. Moreover, the conventional oxidative stress markers GSH and CAT were decreased significantly by 13.1 and 23.4%, respectively, while TBARS and CARB were increased significantly by 26.1 and 15.6%, respectively, after the race indicating oxidative stress induction. Discussion The present study demonstrated for the first time that the RedoxSYS diagnostic system can be used for evaluating the exercise-induced oxidative stress in athletes. PMID:25494543

  9. Low reduction potential of Ero1? regulatory disulphides ensures tight control of substrate oxidation

    PubMed Central

    Baker, Karl M; Chakravarthi, Seema; Langton, Kevin P; Sheppard, Alyson M; Lu, Hui; Bulleid, Neil J

    2008-01-01

    Formation of disulphide bonds within the mammalian endoplasmic reticulum (ER) requires the combined activities of Ero1? and protein disulphide isomerase (PDI). As Ero1? produces hydrogen peroxide during oxidation, regulation of its activity is critical in preventing ER-generated oxidative stress. Here, we have expressed and purified recombinant human Ero1? and shown that it has activity towards thioredoxin and PDI. The activity towards PDI required the inclusion of glutathione to ensure sustained oxidation. By carrying out site-directed mutagenesis of cysteine residues, we show that Ero1? is regulated by non-catalytic disulphides. The midpoint reduction potential (E°?) of the regulatory disulphides was calculated to be approximately ?275 mV making them stable in the redox conditions prevalent in the ER. The stable regulatory disulphides were only partially reduced by PDI (E°???180 mV), suggesting either that this is a mechanism for preventing excessive Ero1? activity and oxidation of PDI or that additional factors are required for Ero1? activation within the mammalian ER. PMID:18971943

  10. 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

  11. Electrode measurements of the oxidation reduction potential in the Gotland Deep using a moored profiling instrumentation

    NASA Astrophysics Data System (ADS)

    Meyer, David; Prien, Ralf D.; Dellwig, Olaf; Waniek, Joanna J.; Schulz–Bull, Detlef E.

    2014-03-01

    The Gotland Deep Environmental Sampling Station (GODESS) operating between 30 m and 185 m was used to assess the variation of in situ redox potential (Eh) in the stratified water column of the central Baltic Sea, for a period of 56 days (November 2010-January 2011). The aim of this study was to acquire in-depth understanding of redox variations with the overall objective to identify the processes controlling Eh. At an interval of 8 h basic hydro-physical parameters were registered, including the oxidation-reduction potential, dissolved oxygen, chlorophyll a fluorescence, turbidity, temperature and conductivity. In total 170 profiles of all parameters were obtained. The measured Eh (with respect to standard hydrogen electrode, SHE) ranged from -0.055 V to 0.167 V. After temperature and pH correction of the standard reduction potentials, a comparison of the measured Eh with that calculated for the particular redox couples was carried out by applying the Nernst-equation. Furthermore, the concentrations of the most important redox elements such as Fe, Mn, N, O, C and S used for comparison were estimated by using empirical functions or were based on measurements of discrete water samples, taken at the time of deployment and recovery of the mooring. The obtained results reveal that the reduction of Fe(III) and O2 may be the main processes controlling the Eh potential in the Gotland basin. Below the redoxcline the reduction of hematite and then ferric oxyhydroxide could be related to the redox potential and somewhat deeper Fe(III)/Fe(II) was found to be the dominant redox couple. Although mixed potential theory could have been applied, the Fe couples appear to dominate over many other possible redox equilibria. This may be explained by the relatively high exchange current of Fe and by high Fe concentrations (up to 1.5 ?M). Finally, a close correspondence to the Eh potentials measured in the oxic/hypoxic part of the water column was found considering the O2/O2-· and the O2-·/H2O2 couples. This suggests that one-electron transfer reactions determined the Eh under oxic/hypoxic conditions.

  12. The oxidation-reduction potential of aqueous soil solutions at the Mars Phoenix landing site

    NASA Astrophysics Data System (ADS)

    Quinn, Richard C.; Chittenden, Julie D.; Kounaves, Samuel P.; Hecht, Michael H.

    2011-07-01

    Results from the Mars Phoenix mission Wet Chemistry Laboratory (WCL) are used to determine the oxidation-reduction potential (Eh) of the Phoenix WCL Rosy Red sample soil solution. The measured Eh of the Rosy Red sample in the WCL aqueous test solution was 253 ± 6 mV at a pH of 7.7 ± 0.1. Measured solution Eh changes correspond to changes in solution H+ activity, which is controlled mainly by changes in headspace PCO2 and solution CO32-, HCO3-, and CO2 concentrations. If measured at a PCO2 of 8 mbar in water, rather than in WCL test solution, the Eh of the Rosy Red soil solution would be ˜300 mV. The results of laboratory experiments using analog salt mixtures are compatible with the possible presence of low levels (ppm) of metal peroxides or other oxidants and indicate that levels of readily soluble ferrous iron in the soil are below 1 ppm.

  13. NO x monitoring of a simultaneous nitrifying–denitrifying (SND) activated sludge plant at different oxidation reduction potentials

    Microsoft Academic Search

    Norbert Weissenbacher; Christian Loderer; Katharina Lenz; Susanne N. Mahnik; Bernhard Wett; Maria Fuerhacker

    2007-01-01

    Simultaneous nitrification–denitrification (SND) allows biological nitrogen removal in a single reactor without separation of the two processes in time or space but requires adapted control strategies (anoxic\\/aerobic conditions). In this study, the formation of gaseous nitric oxide (NOG) and nitrogen dioxide (NO2G) was monitored for SND in relation to the oxidation-reduction potential (ORP) and nitrogen removal in a lab batch

  14. 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.

  15. Use of ORP (oxidation-reduction potential) to control oxygen dosing for online sulfide oxidation in anaerobic treatment of high sulfate wastewater

    Microsoft Academic Search

    S. K. Khanal; C. Shang; J.-C. Huang

    2003-01-01

    In this study, oxidation-reduction potential (ORP) was used as a controlling parameter to regulate oxygen dosing to the recycled biogas for online sulfide oxidation in an upflow anaerobic filter (UAF) system. The UAF was operated with a constant influent COD of 18,000 mg\\/L, but with different influent sulfates of 1000, 3000 and 6000 mg\\/L. The reactor was initially operated under

  16. Real-time treatment of dairy manure: Implications of oxidation reduction potential regimes to nutrient management strategies

    Microsoft Academic Search

    Asif Qureshi; K. Victor Lo; Ping H. Liao; Donald S. Mavinic

    2008-01-01

    A pilot-scale sequencing batch reactor (SBR) was operated at a dairy farm to test real-time based control in winter operation conditions. A combination of high loading and low oxidation reduction potential (ORP) conditions in the aerobic stage of SBR treatment (an end value of ?50 to ?150mV) inhibited nitrification while maintaining carbon removal. After a period of over-aeration over several

  17. [PH and oxidation-reduction potential change of environment during a growth of lactic acid bacteria: effects of oxidizers and reducers].

    PubMed

    Sogomonian, D; Akopian, K; Trchunian, A

    2011-01-01

    Decrease of pH and dropping of oxidation-reduction potential have been observed during growing Lactobacillus salivarius 1588 and 3823, Lactobacillus acidophilus 101E, and Lactococcus lactis 3690 in anaerobic conditions in medium with glucose acidification. These parameters and membrane proton permeability of bacteria (C(M)(H+)) changed in the mediums with different pH. Oxidizer ferrycianide and reducer DL-dithiothreitol affected the bacterial growth and their changed H+ extrusion from the cells and K+ uptake by the cells in experiment conditions. Application of oxidizers and reducers are suggested for regulation of growth related with H+ ion transport in lactic acid bacteria. PMID:21442918

  18. Control of the site and potential of reduction and oxidation processes in pi-expanded quinoxalinoporphyrins.

    PubMed

    Sintic, Paul J; E, Wenbo; Ou, Zhongping; Shao, Jianguo; McDonald, James A; Cai, Zheng-Li; Kadish, Karl M; Crossley, Maxwell J; Reimers, Jeffrey R

    2008-01-14

    Quinoxalino[2,3-b]porphyrins are pi-expanded porphyrins, having a quinoxaline fused to a beta,beta-pyrrolic position of the porphyrin. They are used as components in systems proposed as molecular wires. Knowledge of their redox properties is of value in the design of electron- or hole-conduction systems. In particular, the location of the charge density in the radical anions of quinoxalinoporphyrins can be modulated by peripheral functionalization. New theoretical treatments of electrochemical potentials are developed that identify the site of reduction in both the anions and the dianions of 33 quinoxalinoporphyrins. These molecules include free-base and metallated macrocycles substituted on the quinoxaline with electron-withdrawing groups (NO2, Cl, Br) and/or electron-donating groups (NH2, OCH3). Spectroelectrochemistry, density-functional theory calculations, and substituent-parameter models are used to verify the analysis. Five distinct patterns are observed for the locations of the first and second reductions; some of these patterns involve delocalized charges. Nitroquinoxalinoporphyrins with the nitro groups at the 5- and 6-quinoxaline positions are found to have quite different properties owing to distortions caused by peri interactions that force the nitro group of the 5-nitro regioisomer out of conjugation. Charge localization on the nitroquinoxaline fragment is found for some molecules, and this is attributed to ion-pairing with the 0.1 M tetrabutylammonium perchlorate electrolyte used, leading to the verified prediction that electron-paramagnetic resonance spectra of these molecules taken without the electrolyte yield delocalized anions. These properties enable the control of conduction through molecular wires synthesised from quinoxalinoporphyrins. PMID:18273994

  19. Oxidation-reduction potentials in a salt marsh: Spatial patterns and interactions with primary production

    Microsoft Academic Search

    BRIAN L. HOWES; ROBERT W. HOWARTH; JOHN M. TEAL; IVAN VALIELA

    1981-01-01

    Spurtina alterniflora oxidizes the sediments in which it grows through both passive oxygen release and active metabolic processes. Eh is higher in the root zone of this grass than in the sediment below the root zone or in unvegetated sediments. Sediments underlying the tall form of S. aZterniJorcl are more oxidized than those under the short form, and sediment redox

  20. 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

  1. Reversible potentials for steps in methanol and formic acid oxidation to CO2; adsorption energies of intermediates on the ideal electrocatalyst for methanol oxidation and CO2 reduction.

    PubMed

    Anderson, Alfred B; Asiri, Haleema Aied

    2014-06-14

    Quantum chemical theory is used to identify the reasons for platinum's limitations as an electrocatalyst for oxidizing methanol at fuel cell anodes. The linear Gibbs energy relation (LGER) method is employed to predict reversible potentials for reaction steps for intermediates on the electrode surface. In this procedure, standard reversible potentials are calculated for the reactions in bulk solution phase and then they are perturbed using calculated adsorption bond strengths to the electrode surface, yielding the equilibrium potentials for each electron transfer step for adsorbed intermediates. Adsorption properties of ideal electrocatalysts for the methanol oxidation are found by imposing the condition that the reversible potential of each electron transfer step equals that for the overall reaction. The adsorption bond strengths that provide the ideal properties also apply to formic acid oxidation and carbon dioxide reduction. It is instructive to think of the ideal electrocatalyst as a lens that focusses the reversible potentials for the n individual electron transfer steps to the reversible potential for the n-electron process. It is found that the ideal catalyst will adsorb many intermediates, including HOOC, CO, OCH, HOC, HOCH, HOCH2, and OCH3 more weakly than platinum, and OOCH and OH more strongly. For example, for one possible pathway it is necessary to weaken adsorption bond strengths for HOCH2, HOCH, OCH, HOOC by about 0.5 eV, weaken adsorption CO by about 1.1 eV and strengthen OH adsorption by about 0.6 eV. These results imply a need for developing new multi-component catalysts. PMID:24741672

  2. NOx monitoring of a simultaneous nitrifying-denitrifying (SND) activated sludge plant at different oxidation reduction potentials.

    PubMed

    Weissenbacher, Norbert; Loderer, Christian; Lenz, Katharina; Mahnik, Susanne N; Wett, Bernhard; Fuerhacker, Maria

    2007-01-01

    Simultaneous nitrification-denitrification (SND) allows biological nitrogen removal in a single reactor without separation of the two processes in time or space but requires adapted control strategies (anoxic/aerobic conditions). In this study, the formation of gaseous nitric oxide (NO(G)) and nitrogen dioxide (NO(2G)) was monitored for SND in relation to the oxidation-reduction potential (ORP) and nitrogen removal in a lab batch reactor and a pilot membrane bio-reactor (MBR). In addition hospital wastewater (COD/N(tot)>6:1) was treated on site for 1 year. The highest total nitrogen removal rates of max 90% were reached at 220-240mV ORP (given as E(h)) with corresponding maximal NO(G) emissions rates of 0.9microgg(-1)VSSh(-1). The maximal emission rates of NO(2G) (0.2microgg(-1)VSSh(-1)) were reached at the same ORP level and the NO(2G) emissions correlated to the nitrite accumulation in the activated sludge up to 5mgl(-1)NO(2L)-N. It was shown that this correlation was due to biological production and not due to pH-dependent chemical conversion. Therefore, NO(2G) can be used as additional control loop for ORP-controlled SND systems to avoid the inhibition of denitrification and high nitrite concentrations in the plant effluent. PMID:17166541

  3. Electrode measurements of the oxidation-reduction potential in the Gotland Deep using medium-term moored profiling instrumentation

    NASA Astrophysics Data System (ADS)

    Meyer, David; Prien, Ralf; Dellwig, Olaf; Schulz-Bull, Detlef

    2013-04-01

    The variation of in situ redox potential (Eh) was studied in the stratified water column (30 - 185 m) of the central Baltic Sea, for a period of 56 days (November, 2010 - January, 2011) using the Gotland Deep Environmental Sampling Station (GODESS) in order to identify the processes that control Eh. During the deployment of the mooring 170 profiles of hydro-physical parameters were registered, including the oxidation-reduction potential, pH, dissolved oxygen, chlorophyll a fluorescence, turbidity, temperature and conductivity. In general, the measured Eh (with respect to standard hydrogen electrode, SHE) ranged from - 55 to 167 mV. A comparison of the measured Eh with that calculated for the particular redox couples was carried out by applying the Nernst-equation. The standard reduction potentials were corrected for temperature and pH. Furthermore, the concentrations of the most important redox components such as Fe, Mn, N, O, C and S used for comparison were estimated by using empirical functions or were based on measurements of discrete water samples, taken at the time of deployment and recovery of the mooring. The results reveal that the reduction of Fe(III) essentially controls the electrode potential of the redox sensor in most parts of the anoxic waters. Below the redoxcline the reduction of hematite and then ferric oxyhydroxid could be related to the redox potential and somewhat deeper Fe(III)/Fe(II) was found to be the dominant redox couple. Theoretically a mixed potential theory should have been applied because in natural waters a variety of redox pairs is present but Fe couples appear to dominate all the other redox equlibria. This could be explained by the relatively high exchange current of Fe and by the high concentrations (up to 1.5 µM) present at those depths in the study area. However, there are still gaps in our knowledge about the cycling of redox-sensitive elements and long-term moored profiling instrumentations may help to improve our understanding. Thus, we are pursuing the use of in situ analyzers for electro active compounds on moored systems in the future. In this case, analyzer data would be associated with chemical and physical parameters measured with high resolution in time and space, giving information on mixing processes and reaction kinetics. This approach is required to assess the relevance, for instance, of intrusions of oxygenated waters, vertical eddy-diffusion and fluctuations caused by internal waves on the cycle of redox-sensitive elements. This is particularly important as lateral transport appears to play a dominant role along isopycnal surfaces, especially in medium-sized stratified basins and yet have not been investigated extensively in the Baltic Sea with respect to the cycles of the most electro-active compounds.

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

    PubMed

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

    2015-01-01

    One-stage autoheated thermophilic aerobic digestion (ATAD) can stabilize sludge to meet class A standard. In this study, batch experiments were conducted to investigate the characteristics of oxidation-reduction potential (ORP), volatile fatty acids (VFAs), soluble chemical oxygen demand (SCOD), and nutrients at different temperatures (45, 55, and 65 °C) in the one-stage ATAD. Results showed that the ORP values remained between approximately -350 and -120 mV in the primary 5-day digestion despite of excessive aeration in the digester, indicating that the aeration level could be decreased in an ATAD system to save energy. The pH exhibited a poor correlation (R (2)?

  5. Real-time treatment of dairy manure: implications of oxidation reduction potential regimes to nutrient management strategies.

    PubMed

    Qureshi, Asif; Lo, K Victor; Liao, Ping H; Mavinic, Donald S

    2008-03-01

    A pilot-scale sequencing batch reactor (SBR) was operated at a dairy farm to test real-time based control in winter operation conditions. A combination of high loading and low oxidation reduction potential (ORP) conditions in the aerobic stage of SBR treatment (an end value of -50 to -150 mV) inhibited nitrification while maintaining carbon removal. After a period of over-aeration over several cycles, the ORP at the end of the aerobic stage increased to values of 50-75 mV. Subsequently, nitrification was observed, accompanied by higher total cycle times. Significant increase in removal efficiencies of ammonical nitrogen (alpha<0.0001) and chemical oxygen demand (alpha<0.001) were observed for the high ORP phase. It is postulated that higher ORP regimes are needed for nitrification. In low ORP regimes, nitrification is absent or occurs at an extremely low rate. It is also noted that nitrifying systems treating high strength animal manure can possibly lead to unacceptably high levels of effluent nitrate+nitrite nitrogen (NO(x)-N). Two manure management schemes are proposed that give the farmer an option to either retain the nutrients, or remove them from the wastewater. Some advantages and disadvantages of the schemes are also discussed. PMID:17467983

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

    NASA Astrophysics Data System (ADS)

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

    1995-03-01

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

  7. 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.

  8. [Growth and proton-potassium exchange in Enterococcus hirae: protonophore effect and the role of oxidation-reduction potential].

    PubMed

    Poladian, A; Kirakosian, G; Trchunian, A

    2006-01-01

    Enterococcus hirae ATCC 9790 are able to grow under anaerobic conditions during the fermentation of sugars (pH 8.0) in the presence of the protonophore carbonylcyanide-m-chlorophenylhydrazone at a lesser specific growth rate. As bacteria grow, the acidification of the external medium and a drop in the redox potential from positive to negative (up to -220 mV) values occur. The reducer dithiothreitol, which maintains the negative values of the redox potential, increases the growth rate and acidification of the medium, recovering thereby the effect of the protonophore (without interacting with it). Conversely, the impermeable oxidizer ferricyanide, while maintaining positive values of the redox potential, inhibits the bacterial growth. These results indicate the role of the proton-motive force and importance of reducing processes in bacterial growth. The proton-potassium exchange is inhibited by carbonylcyanide-m-chlorophenylhydazone but is restored with dithiothreitol. Dithiothreiol is able to substitute the proton-motive force; however, ferricyanide and dithiothreitol may also directly affect the bacterial membrane. PMID:16808350

  9. 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.

  10. Recent biocatalytic oxidation–reduction cascades

    PubMed Central

    Schrittwieser, Joerg H; Sattler, Johann; Resch, Verena; Mutti, Francesco G; Kroutil, Wolfgang

    2011-01-01

    The combination of an oxidation and a reduction in a cascade allows performing transformations in a very economic and efficient fashion. The challenge is how to combine an oxidation with a reduction in one pot, either by running the two reactions simultaneously or in a stepwise fashion without isolation of intermediates. The broader availability of various redox enzymes nowadays has triggered the recent investigation of various oxidation–reduction cascades. PMID:21130024

  11. 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.

  12. 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 ...

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

    Microsoft Academic Search

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

    2007-01-01

    Ultraviolet (UV) disinfection systems are incorporated into drinking water production facilities because of their broad-spectrum antimicrobial capabilities, and the minimal disinfection by-product formation that generally accompanies their use. Selection of an optimal location for a UV system within a drinking water treatment facility depends on many factors; a potentially important consideration is the effect of system location on operation and

  14. Dechlorination by combined electrochemical reduction and oxidation

    Microsoft Academic Search

    CONG Yan-qing; WU Zu-cheng; TAN Tian-en

    Chlorophenols are typical priority pollutants listed by USEPA (U.S. Environmental Protection Agency). The removal of chlorophenol could be carried out by a combination of electrochemical reduction and oxidation method. Results showed that it was feasible to degrade contaminants containing chlorine atoms by electrochemical reduction to form phenol, which was further degraded on the anode by electrochemical oxidation. Chlorophenol removal rate

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

    PubMed

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

    2013-12-01

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

  16. 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 (...

  17. Relationship of arsenic concentration with ammonium-nitrogen concentration, oxidation reduction potential and pH of groundwater in arsenic-contaminated areas in Asia

    NASA Astrophysics Data System (ADS)

    Kurosawa, Kiyoshi; Egashira, Kazuhiko; Tani, Masakazu

    This study examines how arsenic (As) concentration is related to ammonium-nitrogen (NH4-N) concentration, oxidation reduction potential (ORP) and pH in groundwater to determine if they have common characteristics in groundwater with high As concentrations in the As-contaminated areas of Bangladesh, Nepal, Cambodia and Vietnam. For the groundwater samples having the three highest As concentrations (top three groundwaters) selected as representatives at each location, As and NH4-N concentrations varied, but ORP and pH did not vary by locations. The ORP value of 30-110 mV, indicating the reducing condition, and the neutral to slightly alkaline pH (pH 7.0-7.6) were presumed to be the key conditions for high As concentrations in groundwater of the study areas. According to the ORP (Eh)-pH diagram, the dominant As species in the top three groundwaters from each location was hydrogen arsenate (HAsO42-). Out of the correlations between the four elements for the top three groundwaters in the areas, only the correlation between As and NH4-N concentrations was positive and significant. Thus, it was identified that NH4-N had an effect on increasing As concentration in groundwater.

  18. 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

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

    PubMed

    Shiskowskii, D M; Mavinic, D S

    2005-08-01

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

  20. 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.

  1. 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 H2O2) capacities of aquifer solids and groundwater have been made on samples from a sand-and-gravel aquifer. he groundwater contributed less than 1% of the system oxidation or reducti...

  2. Oxidative and reductive transformations of epothilone A

    Microsoft Academic Search

    Michael Sefkow; Michael Kiffe; Dietmar Schummer; Gerhard Höfle

    1998-01-01

    The C7 hydroxy group of cytotoxic epothilone A was selectively oxidized using PDC. A selective oxidation of the C3 hydroxy group was accomplished with Me2S\\/(PhCO2)2 after in situ protection of C7OH. Reduction of epothilone A or of a C5, C7 dioxo derivative with NaBH4 proceeded at the C5 carbonyl group. Oxidation and hydrogenation of the C16C17 double bond proved to

  3. 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.

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

    PubMed Central

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

    2010-01-01

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

  5. 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.

  6. 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

  7. The selective catalytic reduction of nitric oxide with methane over scandium oxide, yttrium oxide and lanthanum oxide

    Microsoft Academic Search

    Mark D Fokema; Jackie Y Ying

    1998-01-01

    The selective catalytic reduction of nitric oxide with methane over nanocrystalline Group IIIB metal oxides was investigated between 400°C and 675°C. Scandium oxide and yttrium oxide are better catalysts than lanthanum oxide because they have a greater specific activity and selectivity. The activity of yttrium oxide is 75% of that of Co-ZSM-5 at 600°C and yttrium oxide was also found

  8. 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.

  9. Reduction Potentials of One-Electron Couples Involving Free Radicals in Aqueous Solution

    Microsoft Academic Search

    Peter Wardman

    1989-01-01

    Reduction of an electron acceptor (oxidant), A, or oxidation of an electron donor (reductant), A2?, is often achieved stepwise via one-electron processes involving the couples A\\/A?? or A??\\/A2? (or corresponding prototropic conjugates such as A\\/AH? or AH?\\/AH2). The intermediate A??(AH?) is a free radical. The reduction potentials of such one-electron couples are of value in predicting the direction or feasibility,

  10. 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...

  11. 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).

  12. Analysis of potential helicopter vibration reduction concepts

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

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

    SciTech Connect

    Burke, L.D.; O'Sullivan, J.F.; O'Dwyer, K.J.; Scannell, R.A.; Ahern, M.J.G.; McCarthy, M.M. (Dept. of Chemistry, Univ. College, Cork (IE))

    1990-08-01

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

  14. Manganese oxide reduction as a form of anaerobic respiration

    Microsoft Academic Search

    Henry L. Ehrlich

    1987-01-01

    Some instances of bacterial manganese oxide reduction observed in nature and under laboratory conditions are a form of respiration. Anaerobiosis is not a necessary condition for its occurrence, although anaerobic reduction of manganese oxide which is inhibited by air has been reported. It is the kind of manganese reducing microorganism involved which determines whether anaerobic conditions are required. In at

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

    SciTech Connect

    Karell, E.J.; Pierce, R.D.; Mulcahey, T.P. [Argonne National lab., IL (United States). Chemical Technology Div.

    1996-05-01

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

  16. 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.

  17. 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.

  18. Electro-catalytic reduction of nitrogen oxides

    Microsoft Academic Search

    McLarnon

    1989-01-01

    Nitrogen oxides have been linked to a broad range of air pollution problems including acid rain and the atmospheric production of photochemical ozone. Over twenty million tons of nitrogen oxides are emitted into the atmosphere each year as a result of the high temperature combustion of fossil fuels. Efforts to control nitrogen oxides emissions have lagged because of the generally

  19. 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…

  20. REDUCTION OF NITRIC OXIDE WITH METAL SULFIDES

    EPA Science Inventory

    The report gives results of research to determine the technical feasibility of using metal sulfide for the chemical reduction of NOx to N2. Nineteen different metal sulfides were investigated, using a test gas of pure NO. Although most sulfides resulted in some NO reduction, BaS,...

  1. Three-Electrode Metal Oxide Reduction Cell

    DOEpatents

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

    2005-06-28

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

  2. 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.

  3. 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

  4. Gaseous reduction of iron oxides: Part IV. mathematical analysis of partial internal reduction-diffusion control

    Microsoft Academic Search

    R. H. Tien; E. T. Turkdogan

    1972-01-01

    In this mathematical analysis of gaseous reduction of iron oxides, the partial internal reduction of the porous oxide and\\u000a gas diffusion in the porous iron layer are considered simultaneously in deriving the rate equation. The rate equation, derived\\u000a by partly analytical and partly numerical solutions, is well substantiated by the experimental results obtained previously.\\u000a The following parameters, determined previously, are

  5. Size-reduction of nanodiamonds via air oxidation

    E-print Network

    T. Gaebel; C. Bradac; J. Chen; P. Hemmer; J. R. Rabeau

    2011-04-27

    Here we report the size reduction and effects on nitrogen-vacancy centres in nanodiamonds by air oxidation using a combined atomic force and confocal microscope. The average height reduction of individual crystals as measured by atomic force microscopy was 10.6 nm/h at 600 {\\deg}C air oxidation at atmospheric pressure. The oxidation process modified the surface including removal of non-diamond carbon and organic material which also led to a decrease in background fluorescence. During the course of the nanodiamond size reduction, we observed the annihilation of nitrogen-vacancy centres which provided important insight into the formation of colour centres in small crystals. In these unirradiated samples, the smallest nanodiamond still hosting a stable nitrogen-vacancy centre observed was 8 nm.

  6. Electrochemical reduction and oxidation of molybdenum oxides in propylene carbonate

    SciTech Connect

    Vereshchagina, I.S.; Tikhanov, K.I.; Makhalov, N.A.

    1982-02-10

    In the search for cathodes that can be used in reversibly functioning power sources with aprotic electrolytes, the molybdenum oxide electrode was revealed as promising. The high specific energy of power sources based on the Li-MoO/sub 3/ system and the cycling performance of the MoO/sub 3/ electrode have been pointed out. However, little is known concerning the processes taking place at the electrode and concerning the factors influencing reversibility of the electrodes. It was the aim of the present work to examine the electrochemical behavior of the molybdenum oxide electrode in 1 M LiClO/sub 4/ solution in propylene carbonate (PC) during cycling.

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

    SciTech Connect

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

    1989-09-05

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

  8. 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.

  9. Pharmacological potential of cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Celardo, Ivana; Pedersen, Jens Z.; Traversa, Enrico; Ghibelli, Lina

    2011-04-01

    Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxide nanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles between the Ce3+ and Ce4+ oxidation states allow nanoceria to react catalytically with superoxide and hydrogen peroxide, mimicking the behavior of two key antioxidant enzymes, superoxide dismutase and catalase, potentially abating all noxious intracellular reactive oxygen species (ROS) via a self-regenerating mechanism. Hence nanoceria, apparently well tolerated by the organism, might fight chronic inflammation and the pathologies associated with oxidative stress, which include cancer and neurodegeneration. Here we review the biological effects of nanoceria as they emerge from in vitro and in vivo studies, considering biocompatibility and the peculiar antioxidant mechanisms.

  10. 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.

  11. Nitrogen oxides reduction by staged combustion of LCV gas 

    E-print Network

    Cabrera Sixto, Jose Manuel

    1990-01-01

    of nitrogen that can be present in the ambient air: nitric oxide (NO), nitrogen dioxide (NO z), nitrous oxide (NzO), unsymmetrical nitrogen trioxide (OONO), symmetrical nitrogen trioxide (ON(D P ), dinitrogen trioxide (N zO s), dinitrogen tetroxide (NzO4... NITROGEN OXIDES REDUCTION BY STAGED COMBUSTION OF LCV GAS by JOSE MANUEL CABRERA SIXTO Submitted to the Of6ce of Graduate Studies of Texas A dt M University. in partial ful6llment of the requirements for the degree of MASTER OF SCIENCE...

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

    USGS Publications Warehouse

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

    1996-01-01

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

  13. Experimental study on nitric oxide reduction through calcium propionate reburning

    Microsoft Academic Search

    Shengli Niu; Kuihua Han; Jianli Zhao; Chunmei Lu

    2011-01-01

    Performances of calcium propionate (CP) on nitric oxide (NO) reduction are experimentally investigated on a drop tube furnace system from basic reburning (BR), Thermal De-NOx and advanced reburning (AR) and it is demonstrated to be feasible of using CP as reburning fuel. BR could supply about 80% efficiency with reburning fuel fraction (Rff) and residence time (?) kept 20–25% and

  14. Chemical etching of manganese oxides for electrocatalytic oxygen reduction reaction.

    PubMed

    Lei, Kaixiang; Han, Xiaopeng; Hu, Yuxiang; Liu, Xue; Cong, Liang; Cheng, Fangyi; Chen, Jun

    2015-07-25

    Mixed-valent MnOx (1 < x < 2) was selectively synthesized by chemically etching MnO and Mn2O3 with ceric ammonium nitrate. The obtained MnOx exhibited greatly enhanced electrocatalytic activity toward the oxygen reduction reaction (ORR) as compared to the corresponding pristine oxides. PMID:26097914

  15. Mechanisms of oxidative vs. reductive nitrobenzene transformation by microorganisms

    Microsoft Academic Search

    Ivo Caravatti; Thomas Hofstetter

    Nitroaromatic compounds such as nitrobenzene (NB), are widespread environmental contaminants. In natural attenuation processes selected microorganisms are able to degrade nitrobenzene via two different pathways, that is oxidation of nitrobenzene to catechol and reduction to aniline, respectively. Since both processes occur under oxic conditions but the latter leads to products of similar toxicity than the initial contaminant, it is necessary

  16. Cost-reduction potential in LMFBR design

    SciTech Connect

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

    1983-01-01

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

  17. Tyrosine can protect against oxidative stress through ferryl hemoglobin reduction.

    PubMed

    Lu, Naihao; He, Yingjie; Chen, Chao; Tian, Rong; Xiao, Qiang; Peng, Yi-Yuan

    2014-08-01

    The toxic mechanism of hemoglobin (Hb) under oxidative stress is linked to the formations of highly cytotoxic ferryl species and subsequently heme-to-protein cross-linked derivative of Hb (Hb-X). In this study, we have examined the effects of free tyrosine and its analogues (3-chlorotyrosine, phenylalanine) on the stability of ferryl hemoglobin and the formation of Hb-X. The results showed that free tyrosine (not phenylalanine, 10-500 ?M) was an efficient reducing agent of ferryl species and also effective at preventing the formation of cytotoxic Hb-X. Meanwhile, the dimeric tyrosine was formed as the oxidation product of tyrosine during Hb redox reaction. Compared with free tyrosine, 3-chlorotyrosine, an oxidation product of tyrosine and a proposed biomarker for hypochlorous acid (HOCl) in vivo, exhibited stronger antioxidant properties in Hb-induced oxidative stress, which was consistent with its more efficient ability in the reduction of ferryl species. These results showed that the presence of tyrosine and its derivative in vivo and vitro could ameliorate oxidative damage through ferryl heme reduction. The antioxidant ability, therefore, may provide new insights into the nutritional and physiological significance of free tyrosine with redox active heme proteins-related oxidative stress. PMID:24698734

  18. Pharmacological potential of cerium oxide nanoparticles

    Microsoft Academic Search

    Ivana Celardo; Jens Z. Pedersen; Enrico Traversa; Lina Ghibelli

    2011-01-01

    Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxide nanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles

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

    ERIC Educational Resources Information Center

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

    1989-01-01

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

  20. 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.

  1. Selective catalytic reduction of nitric oxide with ammonia over silica-supported vanadium oxide catalyst

    SciTech Connect

    Qajar, J.; Mowla, D. [Shiraz University, Shiraz (Iran)

    2009-07-01

    The selective catalytic reduction (SCR) of nitric oxide with excess ammonia in the presence of oxygen on silica-supported vanadium oxide catalyst was studied in a packed-bed reactor, and a mathematical model was proposed for the processes occurring in the reactor. Experimental data were presented for evaluation of the accuracy of the proposed model. Good agreement was observed between the measured and calculated values of the conversion in the outlet of the reactor. Once the validity of the proposed model was verified, it was used to examine the effects of different parameters such as feed temperature, inlet feed composition, and gas hourly space velocity (GHSV) on the conversion of NO over V{sub 2}O{sub 5}/SiO{sub 2} catalyst for practical application. The results for the employed catalyst showed that high NO conversion occurred at temperatures of 280-300C, GHSV less than 2000h{sup -1} (STP), and O{sub 2} concentration greater than 10% v/v. These results clearly demonstrate the high potential for this catalyst to be applied commercially for the control of NOx emissions from flue gases of different sources.

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

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

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

  3. Mechanistic study of the selective catalytic reduction of nitric oxide with methane over yttrium oxide

    SciTech Connect

    Fokema, M.D.; Ying, J.Y.

    2000-05-15

    The catalytic activity of nanocrystalline Group IIIB metal oxides for the reduction of nitric oxide with methane was shown to be comparable to that of Co-ZSM-5. The mechanism of selective catalytic reduction of nitric oxide with methane in excess oxygen was examined over nanocrystalline yttrium oxide. A series of heterogeneous and homogeneous reaction steps was proposed to account for the observed trends in catalytic properties. Methyl radicals generated at the catalyst surface desorb into the gas phase, where they react with nitric oxide to form nitrosomethane. Nitrosomethane then decomposes in a series of homogeneous and heterogeneous reactions to produce nitrogen and nitrous oxide. Evidence for gas-phase reaction of methyl radicals with nitric oxide was found in the adsorption studies of nitric oxide on yttrium oxide, the presence of ethane and ethene in the reactor effluent, catalytic studies involving nitrosomethane and nitromethane, as well as the successful prediction of methane selectivities based on a homogeneous reaction mechanism for methyl radical consumption. The proposed pathway for nitrogen production was supported by the observation of hydrogen cyanide under certain operating conditions, as well as adsorbed NCO species detected by infrared spectroscopy.

  4. Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

    PubMed

    Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

    2014-06-01

    Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., ?-FeOOH, ?-FeOOH, ?-Fe2O3 and ?-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or ?-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. PMID:24703664

  5. 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.

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

    SciTech Connect

    Wan, Wubo [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Zhao, Zongbin, E-mail: zbzhao@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Hu, Han [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Gogotsi, Yury [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Department of Materials Science and Engineering, and A.J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, PA 19104 (United States); Qiu, Jieshan, E-mail: jqiu@dlut.edu.cn [Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2013-11-15

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

  7. 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.

  8. Pathogenesis of Chronic Hyperglycemia: From Reductive Stress to Oxidative Stress

    PubMed Central

    Yan, Liang-Jun

    2014-01-01

    Chronic overnutrition creates chronic hyperglycemia that can gradually induce insulin resistance and insulin secretion impairment. These disorders, if not intervened, will eventually be followed by appearance of frank diabetes. The mechanisms of this chronic pathogenic process are complex but have been suggested to involve production of reactive oxygen species (ROS) and oxidative stress. In this review, I highlight evidence that reductive stress imposed by overflux of NADH through the mitochondrial electron transport chain is the source of oxidative stress, which is based on establishments that more NADH recycling by mitochondrial complex I leads to more electron leakage and thus more ROS production. The elevated levels of both NADH and ROS can inhibit and inactivate glyceraldehyde 3-phosphate dehydrogenase (GAPDH), respectively, resulting in blockage of the glycolytic pathway and accumulation of glycerol 3-phospate and its prior metabolites along the pathway. This accumulation then initiates all those alternative glucose metabolic pathways such as the polyol pathway and the advanced glycation pathways that otherwise are minor and insignificant under euglycemic conditions. Importantly, all these alternative pathways lead to ROS production, thus aggravating cellular oxidative stress. Therefore, reductive stress followed by oxidative stress comprises a major mechanism of hyperglycemia-induced metabolic syndrome. PMID:25019091

  9. 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.

  10. Isoniazid: Radical-induced oxidation and reduction chemistry.

    PubMed

    Rickman, Kimberly A; Swancutt, Katy L; Mezyk, Stephen P; Kiddle, James J

    2013-05-15

    Isoniazid is a potent and selective therapeutic prodrug agent used to treat infections by Mycobacterium tuberculosis. Although it has been used clinically for over five decades its full mechanism of action is still being elucidated. Essential to its mechanism of action is the activation of isoniazid to a reactive intermediate, the isonicotinyl acyl radical, by the catalase-peroxidase KatG. The isonicotinyl acyl radical then reacts with NAD producing an inhibitor of the NADH-dependent enoyl ACP reductase responsible for mycolic acid synthesis as its primary target. However, the initial oxidation of isoniazid by KatG has also revealed alternative reaction pathways leading to an array of carbon-, oxygen-, and nitrogen-centered radical intermediates. It has also been reported that isoniazid produces nitric oxide in the presence of KatG and hydrogen peroxide. In this study, the temperature-dependent rate constants for the hydroxyl radical oxidation and solvated electron reduction of isoniazid and two model compounds have been studied. Based on these data the initial oxidation of isoniazid by the hydroxyl radical has been shown to predominantly occur at the primary nitrogen of the hydrazyl moiety, consistent with the postulated mechanism for the formation of the isonicotinyl radical. The hydrated electron reduction occurred mostly at the pyridine ring. Concomitant EPR spin-trap measurements under a variety of oxidizing and reducing conditions did not show any evidence of nitric oxide production as had been previously reported. Finally, examination of the transient absorption spectra obtained for hydrated electron reaction with isoniazid demonstrated for the first time an initial reduced transient identified as the isonicotinyl acyl radical produced from isoniazid. PMID:23562055

  11. Adaptive stimulus artifact reduction in noncortical somatosensory evoked potential studies

    Microsoft Academic Search

    Vijay Parsa; Philip A. Parker; Robert N. Scott

    1998-01-01

    Somatosensory evoked potentials (SEP's) are an important class of bioelectric signals which contain clinically valuable information. The surface measurements of these potentials are often contaminated by a stimulus evoked artifact. The stimulus artifact (SA), depending upon the stimulator and measurement system characteristics, may obscure some of the information carried by the SEP's. Conventional methods for SA reduction employ hardware-based circuits

  12. Oxide Reduction in Advanced Metal Stacks for Microelectronic Applications Wentao Qin, Alex A. Volinsky1

    E-print Network

    Volinsky, Alex A.

    Oxide Reduction in Advanced Metal Stacks for Microelectronic Applications Wentao Qin, Alex A used for microelectronic interconnect applications. Interfacial oxides can cause device performance degradation and failure by significantly increasing electrical resistance. Interfacial oxide layers found

  13. 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

  14. Potential role of bicarbonate during pyrite oxidation

    SciTech Connect

    Evangelou, V.P.; Holt, A. [Univ. of Kentucky, Lexington, KY (United States). Dept. of Agronomy] [Univ. of Kentucky, Lexington, KY (United States). Dept. of Agronomy; Seta, A.K. [Univ. Bengkulu (Indonesia). Fakultas Pertanian] [Univ. Bengkulu (Indonesia). Fakultas Pertanian

    1998-07-15

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

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

    SciTech Connect

    Halder, S.; Fruehan, R.J. [Praxair Inc., Tonawanda, NY (United States). Praxair Technological Center

    2008-12-15

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

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

    Microsoft Academic Search

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

    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 85 nm thick La{sub 0.8}Sr{sub 0.2}CoO{sub 3-} (LSC) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia

  17. 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.

  18. Sulfidation and reduction of zinc titanate and zinc oxide sorbents for injection in gasifier exit ducts

    Microsoft Academic Search

    K. Ishikawa; C. Krueger; M. Flytzani-Stephanopoulos; W. Jl; R. J. Higgins; B. A. Bishop; R. L. Goldsmith

    1995-01-01

    The sulfidation reaction kinetics of fine particles of zinc titanate and zinc oxide with HâS were studied in order to test the potential of the sorbent injection hot-gas desulfurization process. Fine sorbent particles with diameter between 0.3 and 60 μm were sulfided with HâS and\\/or reduced with Hâ in a laminar flow reactor over the temperature range of 500-900°C. Sulfidation\\/reduction

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  1. Rate Dependency of Silver Vanadium Phosphorous Oxide Reduction

    NASA Astrophysics Data System (ADS)

    Cheng, Po-Jen

    2011-12-01

    The silver vanadium phosphorus oxide (Ag2VO2PO 4) is a high-capacity and good-compatibility material for the cathode in the battery. Due to their innovative properties, they are used as cathode in lithium batteries. Therefore, when the lithium batteries begin to discharge, the anodes of the cell perform an electrochemical oxidation and release electrons. In the mean time, the cathodes in the cells perform the electrochemical reduction and catch the electrons. For reduction of Ag2VO2PO 4, two silver ions (Ag+) catch two electrons to form silver particles, and the vanadium ions (V5+) catch two electrons to form V3+. It means that four electrons will be released by lithium anode. We call this four electrons discharge as 100% discharge. In my most of the projects, the Ag2VO2PO4 material is tested by differential scanning calorimetry (DSC) to check purity. My study is based on the discharge of batteries, and I focus on the morphology and the intensity of silver particles on the cathode after discharge. Depending on different adjustment of factors, such as discharge time, discharge rate, storage time, storage temperature, I try to investigate the silver intensity, conductivity as a function of DOD (Depth of Discharge). The silver particles could be examined by optical microscope, and scanning electron microscope (SEM). Moreover, I do some x-ray diffraction analysis to quantify the silver particles after discharge. Also, I perform magnetic susceptibility measurement to check the mechanism of the reduction of vanadium ions. Under the research on silver ions and vanadium ions, I will know a big frame of reduction process on silver vanadium phosphorous oxide and the time effect on this cathode material.

  2. Nitrogen loss from soil through anaerobic ammonium oxidation coupled to iron reduction

    NASA Astrophysics Data System (ADS)

    Yang, Wendy H.; Weber, Karrie A.; Silver, Whendee L.

    2012-08-01

    The oxidation of ammonium is a key step in the nitrogen cycle, regulating the production of nitrate, nitrous oxide and dinitrogen. In marine and freshwater ecosystems, anaerobic ammonium oxidation coupled to nitrite reduction, termed anammox, accounts for up to 67% of dinitrogen production. Dinitrogen production through anaerobic ammonium oxidation has not been observed in terrestrial ecosystems, but the anaerobic oxidation of ammonium to nitrite has been observed in wetland soils under iron-reducing conditions. Here, we incubate tropical upland soil slurries with isotopically labelled ammonium and iron(III) to assess the potential for anaerobic ammonium oxidation coupled to iron(III) reduction, otherwise known as Feammox, in these soils. We show that Feammox can produce dinitrogen, nitrite or nitrate in tropical upland soils. Direct dinitrogen production was the dominant Feammox pathway, short-circuiting the nitrogen cycle and resulting in ecosystem nitrogen losses. Rates were comparable to aerobic nitrification and to denitrification, the latter being the only other process known to produce dinitrogen in terrestrial ecosystems. We suggest that Feammox could fuel nitrogen losses in ecosystems rich in poorly crystalline iron minerals, with low or fluctuating redox conditions.

  3. 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.

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

    PubMed

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

    2014-08-13

    Abstract 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

  5. 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.

  6. 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.

  7. Abiotic sulfide oxidation via manganese reduction fuels the deep biosphere

    NASA Astrophysics Data System (ADS)

    Bottrell, S.; Böttcher, M. E.; Schippers, A.; Parkes, R.; Raiswell, R.

    2009-12-01

    The deep biosphere in marine sediments consists of large populations of metabolically active Bacteria and Archaea [1, 2]. Buried organic carbon is the main energy source for the deep biosphere and is anaerobically oxidized via nitrate-, Mn(IV)-, Fe(III)-, sulfate or carbonate-reduction. Sulfate reduction has been identified as the most important of these processes [3, 4] yet sulfate is typically quantitatively removed from pore waters in the upper few meters of marine sediments. A key question remains: “How is continued metabolic activity maintained in the deep biosphere?”. Buried organic carbon remains as an electron donor but the source of electron acceptors is less clear. Stable isotope compositions of sulfur and oxygen in sulfate are particularly useful in the study of biogeochemical processes and sediment-pore fluid interactions e.g. [5, 6]. Here we use stable sulfur and oxygen isotope compositions to show that the oxidant sulfate is generated by anoxic sulfide oxidation in deeply buried sediments of the Cascadia margin and Blake Ridge and controlled anoxic experiments to constrain the mechanisms involved on this reaction. Pore fluid sulfate in deep Cascadia margin and Blake Ridge sediments contained sulfur with similar isotopic composition to diagenetic sulfide in the sediment and oxygen that was depleted in 18O (in some cases depleted in 18O relative to pore water). Experiments with Mn(IV)-containing oxides confirmed that these can abiotically oxidize iron sulfides and also produce sulfate depleted in 18O relative to water. In another set of anoxic experiments, pyrite was mixed with different Fe(III) minerals. Crucially, experiments with synthesized pure Fe(III) minerals produced no sulfate but identical experiments with natural Fe(III) minerals containing trace Mn did. Sulfate concentrations in solution were stoichiometrically balanced by Mn concentrations, showing trace Mn(IV) in the natural minerals to be the oxidizing agent generating sulfate. Sulfate formed was again depleted in 18O relative to water. Experiments with 18O-labelled water show that all oxygen atoms in the sulfate formed are derived from water molecules, thus the sulfate oxygen isotopic composition represents a true fractionation from water. The depletion of 18O in sulfate relative to water thus acts as a fingerprint for sulfate produced by Mn (IV) reduction. Oxidized manganese stored within the mineral fraction of marine sediments can thus drive abiotic anaerobic sulfide oxidation which, together with microbial sulfate reduction, forms a closed sulfur cycle feeding the deep biosphere in marine sediments. [1] Parkes et al. (2005) Nature 436, 390. [2] Schippers et al. (2005) Nature 433, 861. [3] D’Hondt et al. (2002) Science 295, 2067. [4] D’Hondt et al. (2004) Science 306, 2216. Bottrell et al. (2000) J. Geol. Soc. Lond. 157, 711. [6] Böttcher et al. (2006) Proc. ODP Sci. Res. 201-109, 1.

  8. 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

  9. 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

  10. Quinone-enhanced reduction of nitric oxide by xanthine/xanthine oxidase.

    PubMed

    Sanchez-Cruz, Pedro; Alegría, Antonio E

    2009-05-01

    The quinones 1,4-naphthoquinone, methyl-1,4-naphthoquinone, tetramethyl-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,6-dimethylbenzoquinone, 2,6-dimethoxybenzoquinone, and 9,10-phenanthraquinone enhance the rate of nitric oxide reduction by xanthine/xanthine oxidase in nitrogen-saturated phosphate buffer (pH 7.4). Maximum initial rates of NO reduction (V(max)) and the amount of nitrous oxide produced after 5 min of reaction increase with quinone one- and two-electron redox potentials measured in acetonitrile. One of the most active quinones of those studied is 9,10-phenanthraquinone with a V(max) value 10 times larger than that corresponding to the absence of quinone, under the conditions of this work. Because NO production is enhanced under hypoxia and under certain pathological conditions, the observations obtained in this work are very relevant to such conditions. PMID:19301825

  11. Quinone-Enhanced Reduction of Nitric Oxide by Xanthine/Xanthine Oxidase

    PubMed Central

    Sanchez-Cruz, Pedro; Alegría, Antonio E.

    2009-01-01

    The quinones 1,4-naphthoquinone, methyl-1,4-naphthoquinone, tetramethyl-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,6-dimethylbenzoquinone, 2,6-dimethoxybenzoquinone, and 9,10-phenanthraquinone enhance the rate of nitric oxide reduction by xanthine/xanthine oxidase in nitrogen-saturated phosphate buffer (pH 7.4). Maximum initial rates of NO reduction (Vmax) and the amount of nitrous oxide produced after 5 min of reaction increase with quinone one- and two-electron redox potentials measured in acetonitrile. One of the most active quinones of those studied is 9,10-phenanthraquinone with a Vmax value 10 times larger than that corresponding to the absence of quinone, under the conditions of this work. Because NO production is enhanced under hypoxia and under certain pathological conditions, the observations obtained in this work are very relevant to such conditions. PMID:19301825

  12. Continuous Trajectories for Primal-Dual Potential-Reduction Methods

    Microsoft Academic Search

    Reha H. Tutuncu

    This article considers continuous trajectories of the vector elds induced by two dier- ent primal-dual potential-reduction algorithms for solving linear programming problems. For both algorithms, it is shown that the associated continuous trajectories include the central path and the duality gap converges to zero along all these trajectories. For the algorithm of Kojima, Mizuno, and Yoshise, there is a a

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

    SciTech Connect

    Steinberg, N.A.; Oremland, R.S. (Geological Survey, Menlo Park, CA (USA))

    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.

  14. 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.

  15. Ammonium Oxidation and Nitrate Reduction in Sediments of a Hypereutrophic Lake

    E-print Network

    Florida, University of

    Ammonium Oxidation and Nitrate Reduction in Sediments of a Hypereutrophic Lake E. M. D'Angelo and K is through biological oxidation and reduction of N species in the aerobic and anaerobic sediment zones. In continuously stirred batch incubationswith aerated sediment, NHJ oxidation to NOj (nitrification) showed two

  16. The Effect of Iron Oxide on Dissimilatory Nitrate Reduction to Ammonium (DNRA) in Lignin Cellulose medium

    E-print Network

    Vallino, Joseph J.

    The Effect of Iron Oxide on Dissimilatory Nitrate Reduction to Ammonium (DNRA) in Lignin Cellulose that may be more harmful than nitrate. In order to reduce ammonium production I proposed to add iron oxide oxidizing bacteria capable of DNRA. It was concluded that the iron addition actually prevented the reduction

  17. 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).

  18. Hydrogen Reduction of Zinc and Iron Oxides Containing Mixtures

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  19. Reduction characteristics of copper oxide in cerium and zirconium oxide systems

    Microsoft Academic Search

    Lj. Kundakovic; M. Flytzani-Stephanopoulos

    1998-01-01

    The reduction of CuO dispersed on fluorite-type oxide catalysts, namely La-doped CeO2 and Y-doped ZrO2 was studied in this work. On both supports distinct copper species were identified as a function of copper content by temperature-programmed reduction (TPR) by H2 and CH4, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and scanning transmission electron microscopy\\/energy dispersive X-ray (STEM\\/EDX) analyses. At

  20. 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.

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

    PubMed Central

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

    2012-01-01

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

  2. Niobium Oxide-Supported Platinum Ultra-Low Amount Electrocatalysts for Oxygen Reduction

    SciTech Connect

    Sasaki,K.; Zhang, L.; Adzic, R.

    2008-01-01

    We demonstrate a new approach to synthesizing high-activity electrocatalysts for the O2 reduction reaction with ultra low Pt content. The synthesis involves placing a small amount of Pt, the equivalent of a monolayer, on carbon-supported niobium oxide nanoparticles (NbO2 or Nb2O5). Rotating disk electrode measurements show that the Pt/NbO2/C electrocatalyst has three times higher Pt mass activity for the O2 reduction reaction than a commercial Pt/C electrocatalyst. The observed high activity of the Pt deposit is attributed to the reduced OH adsorption caused by lateral repulsion between PtOH and oxide surface species. The new electrocatalyst also exhibits improved stability against Pt dissolution under a potential cycling regime (30000 cycles from 0.6 V to 1.1 V). These findings demonstrate that niobium-oxide (NbO2) nanoparticles can be adequate supports for Pt and facilitate further reducing the noble metal content in electrocatalysts for the oxygen reduction reaction.

  3. 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.

  4. 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

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  6. 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).

  7. 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).

  8. Measuring protein reduction potentials using 15N HSQC NMR spectroscopy.

    PubMed

    Taylor, Samantha L; Crawley-Snowdon, Harriet; Wagstaff, Jane L; Rowe, Michelle L; Shepherd, Mark; Williamson, Richard A; Howard, Mark J

    2013-03-01

    NMR spectroscopy was used to measure reduction potentials of four redox proteins by following multiple (15)N HSQC protein resonances across a titration series using mixtures of oxidised and reduced glutathione. Results for PDI a, PDI ab and DsbA agree with the literature and our result for ERp18 confirms this protein as an oxidoreductase of comparable or greater reducing strength than PDI a. PMID:23360928

  9. Measuring protein reduction potentials using 15N HSQC NMR spectroscopy†

    PubMed Central

    Taylor, Samantha L.; Crawley-Snowdon, Harriet; Wagstaff, Jane L.; Rowe, Michelle L.; Shepherd, Mark; Williamson, Richard A.; Howard, Mark J.

    2015-01-01

    NMR spectroscopy was used to measure reduction potentials of four redox proteins by following multiple 15N HSQC protein resonances across a titration series using mixtures of oxidised and reduced glutathione. Results for PDI a, PDI ab and DsbA agree with the literature and our result for ERp18 confirms this protein as an oxidoreductase of comparable or greater reducing strength than PDI a. PMID:23360928

  10. 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.

  11. 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.

  12. 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.

  13. 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

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

    PubMed

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

    2011-05-01

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

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

    SciTech Connect

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

    2013-10-15

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

  16. 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?.

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

    PubMed

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    Recent observations of methane (CH4) and perchlorate (ClO4-) within the atmosphere and surface of Mars, respectively, provide impetus for establishing a metabolic linkage between these compounds whereby CH4 acts as an electron donor and perchlorate acts as an electron acceptor. Direct linkage through anaerobic oxidation of methane (AOM) has not been observed. However, indirect syntrophic oxygenase-dependent oxidation of CH4 with an aerobic methane oxidizer is feasible. The pathway for anaerobic dissimilatory perchlorate reduction includes 3 steps. The first 2 are sequential reductions of (1) perchlorate to chlorate and (2) chlorate to chlorite, mediated by perchlorate reductase. The third step is disproportionation of chlorite to chloride and molecular oxygen, mediated by chlorite dismutase. Utilization of thusly derived oxygen by hydrocarbon-degrading organisms in anoxic environments was first demonstrated by Coates et. al. (1998)1, however the link to aerobic methane oxidation was not examined at that time. Here, we systematically explore the potential for several species of aerobic methanotrophs to couple with chlorite during dissimilatory perchlorate reduction. In one experiment, 0.5 kPa CH4 was completely removed in one day from the headspace of combined cell suspensions of Dechloromonas agitata strain CKB and Methylococcus capsulatus in the presence of 5 mM chlorite. Oxidation of labeled 14CH4 to 14CO2 under similar conditions was later confirmed. Another experiment demonstrated complete removal of 0.2 kPa CH4 over several days by Methylobacter albus strain BG8 with strain CKB in the presence of 5 mM chlorite. Finally, we observed complete removal of 0.2 kPa CH4 in bottles containing natural soil (enriched in methanotrophs by CH4 additions over several weeks) and strain CKB and in the presence of 10 mM chlorite. This soil, collected from a pristine lake shoreline, demonstrated endogenous methane, perchlorate, chlorate and chlorite uptake. Other soil and sediment environments are being tested for methane oxidation linked either directly or indirectly with perchlorate reduction. 1 Coates, JD, Bruce, Haddock, JD, (1998) Anoxic bioremediation of hydrocarbons. Nature, 396, 730.

  19. Potential oxidative stress due to Pb exposure 

    E-print Network

    Elms, Rene' Davina

    2013-02-22

    The hazards of Pb exposure has been a topic of concern for many years. This research was developed to investigate the possibility of Pb induced oxidative stress. The research objectives were to observe Pb induced lipid ...

  20. Isothermal reduction kinetics of nickel oxide using hydrogen: Conventional and Weibull kinetic analysis

    Microsoft Academic Search

    B. Jankovic

    2007-01-01

    The powder sample of nickel oxide was synthesized by sol–gel procedure. The isothermal reduction of nickel oxide using hydrogen was investigated by thermogravimetric analysis at five operating temperatures: 245, 255, 265, 275 and 300°C. The kinetic triplet (Ea, A and f(?)) was determined using conventional and Weibull kinetic analysis. Both the kinetically procedures show that the reduction process considered can

  1. Thermal analysis of the cyclic reduction and oxidation behaviour of SOFC anodes

    Microsoft Academic Search

    David Waldbillig; Anthony Wood; Douglas G. Ivey

    2005-01-01

    The reduction and oxidation (redox) kinetics of a Ni\\/YSZ cermet were studied at temperatures between 400 and 850 °C by thermogravimetric analysis (TGA) and reduction and oxidation activation energies were determined. In addition, the volume change after redox cycling was examined by thermomechanical analysis (TMA). Samples with fine microstructure similar to a typical SOFC anode functional layer (AFL) and samples

  2. 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

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

    SciTech Connect

    Gao, Zhiming [ORNL] [ORNL; Daw, C Stuart [ORNL] [ORNL; Chakravarthy, Veerathu K [ORNL] [ORNL

    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.

  4. 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

  5. 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

  6. (11,12/94)(4,5/97)(02,3/07)(01/08) Neuman Chapter 17 Oxidation and Reduction

    E-print Network

    Reed, Christopher A.

    Chapter 17 1 17: Oxidation and Reduction 17.1 Oxidation and Reduction Occur Together 17-3 Redox Reactions Involve Electron Transfer (17.1A) 17-3 Inorganic Redox Reactions Organic Redox Reactions Oxidation Levels Presentation of Redox Reactions in this Chapter 17.2 Oxidation of Alcohols and Aldehydes 17-6 Oxidation Using

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

    PubMed Central

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

    2015-01-01

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

  8. Copper oxide reduction by hydrogen under the self-propagation reaction mode

    Microsoft Academic Search

    M. H. Yamukyan; Kh. V. Manukyan; S. L. Kharatyan

    2009-01-01

    In the work the laws of copper oxide, CuO, reduction by hydrogen to metallic copper under the self-propagating mode have been studied. It was shown that reduction process may be performed under the combustion mode even at low hydrogen pressure 0.01MPa. At constant hydrogen pressures the reduction of samples prepared from initial copper oxide occurred under the surface combustion regime

  9. Reduction of chromium oxides in stainless steel dust

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-ling; Guo, Wen-ming; Jia, Xin-lei

    2015-06-01

    The recovery of metal oxides from stainless steel dust using C (graphite), SiFe, and Al as reductants was investigated under various conditions. The apparent distribution ratio of Cr ( L'{Cr/m/s}) in the recovered metal and residual slag phases was defined as the major performance metric. The results show that the recovery ratio of metals increases as the ratio of CaO:SiO2 by mass in the residual slag increases to 1.17. The residual content of metals in the slag decreases as the Al2O3 content of the slag is increased from approximately 8wt% to 10wt%. The recovery ratio of Cr increases with increasing L'{Cr/m/s}, and a linear relationship between L'{Cr/m/s} and the activity coefficient ratio of CrO in the slag and the recovered metal phase is observed. The combination of C and SiFe or Al as the reducing agents reveals that Si is the more effective coreductant.

  10. Recycling of heavy metal alloy turnings to powder by oxidation–reduction process

    Microsoft Academic Search

    He Yuehui; Chen Libao; Huang Baiyun; P. K. Liaw

    2003-01-01

    The processes of direct recycling heavy metal turnings by oxidation–reduction technique have been investigated in details. The average particle size of recycled alloy powders was about 1.5 ?m, and the shape of powder particle was regular when the final reduction temperature was 850 °C. The average size of the particle increased to 5 and 8 ?m when increasing the reduction

  11. Effects of Eh (oxidation potential) on borosilicate waste glass durability

    Microsoft Academic Search

    Jantzen

    1984-01-01

    Solid state materials can be used to control the oxidation potential (Eh) of waste glass leachants. These materials are chosen based on known Eh-pH relations for redox species in the presence of dissolved silica. Experiments under oxidized conditions have enabled evaluation of waste glass durability in the presence of waste package components which affect Eh. 18 references, 4 figures.

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

    SciTech Connect

    Assary, R. S.; Curtiss, L. A.; Redfern, P. C.; Zhang, Z.; Amine, K. (Center for Nanoscale Materials); ( CSE); ( MSD); (Northwestern Univ.)

    2011-06-23

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

  13. Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

    PubMed

    Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

    2015-02-01

    A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. PMID:25176636

  14. 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

  15. Potential Medicare savings through prevention and risk reduction.

    PubMed

    Rula, Elizabeth Y; Pope, James E; Hoffman, Joel C

    2011-02-01

    Medicare is challenged to maintain solvency as enrollment climbs because of the aging baby boomers and costs increase as a result of the substantial disease burden present among seniors. In the present study, an actuarial model was developed to determine the present cost (2008) of Medicare-covered benefits for elderly individuals, and to test the impact on cost of health risk reduction that may be possible through population health and wellness interventions. In the model, beneficiaries were categorized by risk according to health status using 3 different indices, and baseline per month and lifetime expenditures were estimated. Changes in morbidity were tested via scenarios of modified transition rates between the risk categories that might result from population health and wellness initiatives, including increases in the proportion of low-risk individuals entering Medicare, and delayed or reduced rates of upward risk transitions. The model showed that the discounted total lifetime cost of Medicare benefits was $174,018 per person, from age 65 until death. Each risk-reduction scenario was associated with both annual and lifetime cost savings, which accounted for increased longevity associated with decreased risk profiles. In conclusion, a model has been developed that can predict the impact on Medicare costs of varying levels of risk reduction in the senior population and, therefore, the potential financial benefit of population health and wellness policy initiatives directed at improving health prior to and during the years of Medicare. The model shows that there are substantial opportunities for savings through modest improvements to the health of the Medicare population. PMID:21323619

  16. H2O2 Detection at Carbon Nanotubes and Nitrogen-Doped Carbon Nanotubes: Oxidation, Reduction, or Disproportionation?

    PubMed

    Goran, Jacob M; Phan, Ethan N H; Favela, Carlos A; Stevenson, Keith J

    2015-06-16

    The electrochemical behavior of hydrogen peroxide (H2O2) at carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (N-CNTs) was investigated over a wide potential window. At CNTs, H2O2 will be oxidized or reduced at large overpotentials, with a large potential region between these two processes where electrochemical activity is negligible. At N-CNTs, the overpotential for both H2O2 oxidation and reduction is significantly reduced; however, the reduction current from H2O2, especially at low overpotentials, is attributed to increased oxygen reduction rather than the direct reduction of H2O2, due to a fast chemical disproportionation of H2O2 at the N-CNT surface. Additionally, N-CNTs do not display separation between observable oxidation and reduction currents from H2O2. Overall, the analytical sensitivity of N-CNTs to H2O2, either by oxidation or reduction, is considerably higher than CNTs, and obtained at significantly lower overpotentials. N-CNTs display an anodic sensitivity and limit of detection of 830 mA M(-1) cm(-2) and 0.5 ?M at 0.05 V, and a cathodic sensitivity and limit of detection of 270 mA M(-1) cm(-2) and 10 ?M at -0.25 V (V vs Hg/Hg2SO4). N-CNTs are also a superior platform for the creation of bioelectrodes from the spontaneous adsorption of enzyme, compared to CNTs. Glucose oxidase (GOx) was allowed to adsorb onto N-CNTs, producing a bioelectrode with a sensitivity and limit of detection to glucose of 80 mA M(-1) cm(-2) and 7 ?M after only 30 s of adsorption time from a 81.3 ?M GOx solution. PMID:26009497

  17. Insight into the mechanism of the thermal reduction of graphite oxide: deuterium-labeled graphite oxide is the key.

    PubMed

    Sofer, Zden?k; Jankovský, Ond?ej; Šimek, Petr; Sedmidubský, David; Šturala, Ji?í; Kosina, Ji?í; Mikšová, Romana; Macková, Anna; Mikulics, Martin; Pumera, Martin

    2015-05-26

    For the past decade, researchers have been trying to understand the mechanism of the thermal reduction of graphite oxide. Because deuterium is widely used as a marker in various organic reactions, we wondered if deuterium-labeled graphite oxide could be the key to fully understand this mechanism. Graphite oxides were prepared by the Hofmann, Hummers, Staudenmaier, and Brodie methods, and a deuterium-labeled analogue was synthesized by the Hofmann method. All graphite oxides were analyzed not only using the traditional techniques but also by gas chromatography-mass spectrometry (GC-MS) during exfoliation in hydrogen and nitrogen atmospheres. GC-MS enabled us to compare differences between the chemical compositions of the organic exfoliation products formed during the thermal reduction of these graphite oxides. Nuclear analytical methods (Rutherford backscattering spectroscopy, elastic recoil detection analysis) were used to calculate the concentrations of light elements, including the ratio of hydrogen to deuterium. Combining all of these results we were able to determine graphite oxide's thermal reduction mechanism. Carbon dioxide, carbon monoxide, and water are formed from the thermal reduction of graphite oxide. This process is also accompanied by various radical reactions that lead to the formation of a large amount of carcinogenic volatile organic compounds, and this will have major safety implications for the mass production of graphene. PMID:25894311

  18. 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.

  19. Phenylarsine oxide as a redox modulator of transient receptor potential vanilloid type 1 channel function.

    PubMed

    Carlin, Kevin P; Wu, Gang; Patel, Aniket; Crumley, Gregg; Ilyin, Victor I

    2015-02-01

    Transient receptor potential vanilloid type 1 (TRPV1) channels are capable of detecting and integrating noxious stimuli and play an important role in nociceptor activation and sensitization. It has been demonstrated that oxidizing agents are capable of positively modulating (sensitizing) the TRPV1 channel. The present study investigates the ability of the thiol-oxidizing agent phenylarsine oxide (PAO) to modulate TRPV1 currents under voltage-clamp conditions. We assessed the ability of PAO to modulate both proton- and capsaicin-activated currents mediated by recombinant human TRPV1 channels as well as native rat and human TRPV1 channels in dorsal root ganglion (DRG) neurons. Experiments with other oxidizing and reducing agents having various membrane-permeating properties supported the intracellular oxidizing mechanism of PAO modulation. The PAO modulation of proton-activated currents was consistent across the cell types studied, with an increase in current across the proton concentrations studied. PAO modulation of the capsaicin-activated current in hTRPV1/Chinese hamster ovary cells consisted of potentiation of the current elicited with low capsaicin concentrations and inhibition of the current at higher concentrations. This same effect was seen with these recombinant cells in calcium imaging experiments and with native TRPV1 channels in rat DRG neurons. Contrary to this, currents in human DRG neurons were potentiated at all capsaicin concentrations tested after PAO treatment. These results could indicate important differences in the reduction-oxidation modulation of human TRPV1 channels in a native cellular environment. PMID:25250537

  20. 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.

  1. 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.

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

    SciTech Connect

    Crumlin, Ethan [Massachusetts Institute of Technology (MIT); Mutoro, Eva [ORNL; Ahn, Sung Jin [Massachusetts Institute of Technology (MIT); Jose la O', Gerardo [Massachusetts Institute of Technology (MIT); Leonard, Donovan N [ORNL; Borisevich, Albina Y [ORNL; Biegalski, Michael D [ORNL; Christen, Hans M [ORNL; Shao-Horn, Yang [Massachusetts Institute of Technology (MIT)

    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.

  3. 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 ...

  4. CHARACTERIZATION OF OXIDATION-REDUCTION PROCESSES IN CONSTRUCTED WETLANDS FOR SWINE WASTEWATER TREATMENT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Constructed wetlands designed and properly operated for treatment of swine wastewater treatment may enhance oxidation-reduction processes and nutrient treatment performance. The objective of this investigation was to characterize soil wetland processes related to nitrogen (N) treatment (nitrificatio...

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

    EPA Science Inventory

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

  6. Acetylene inhibition of nitrous oxide reduction by denitrifying bacteria

    Microsoft Academic Search

    T. Yoshinari; R. Knowles

    1976-01-01

    Acetylene (0.1 atm) caused complete or almost complete inhibition of reduction of NâO by whole cell suspensions of Pseudomonas perfectomarinus, P. aeruginosa and Micrococcus denitrificans. Acetylene did not inhibit reduction of NOâ⁻ or NOâ⁻ by these organisms. In the presence of acetylene there was stoichiometric conversion of NOâ⁻ or NOâ⁻ to NâO with negligible subsequent reduction of the latter. In

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

    SciTech Connect

    Yuan, Bihe [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou 215123 (China); Bao, Chenlu [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026 (China); Qian, Xiaodong; Wen, Panyue [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou 215123 (China); Xing, Weiyi; Song, Lei [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou 215123 (China)

    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.

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

    SciTech Connect

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

    1998-06-01

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

  9. 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.

  10. 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.

  11. Lightning-induced reduction of phosphorus oxidation state

    Microsoft Academic Search

    Matthew Pasek; Kristin Block

    2009-01-01

    Phosphorus is frequently the limiting nutrient in marine and terrestrial ecosystems, largely owing to its poor solubility and slow movement through the rock cycle. Phosphorus is viewed to exist in geological systems almost exclusively in its fully oxidized state as orthophosphate. However, many microorganisms use the partially oxidized forms-phosphite and hypophosphite-as alternative phosphorus sources, and genomic evidence suggests that this

  12. Effects of the electrode oxidizing potential on underwater wet welds

    SciTech Connect

    Pope, A.M.; Liu, S.; Olson, D.L. [Colorado School of Mines, Golden, CO (United States). Center for Welding and Joining Research

    1994-12-31

    Depth greatly affects the chemical composition and mechanical properties of underwater wet (UWW) welds. It is well documented in the literature that as depth increases, the amount of oxygen in the weld increases while the deoxidants decrease in concentration. To understand the influence of oxygen on the characteristics and properties of UWW welds, deposits of electrodes with different oxidizing potentials were studied. The oxidizing potentials of these electrodes were varied through additions of hematite (Fe{sub 2}O{sub 3}) to the covering of a ruffle electrode. No metallic deoxidants were used in the coverings, but MgO was added to one of the oxidizing electrodes as a possible way to control oxygen. The welds were made at 0.5 m of water depth. Chemical analysis showed that increasing oxidizing potential of the electrodes increased the weld metal oxygen content eventually reaching a plateau value of approximately 2,100 ppm. This concentration plateau is determined by the solubility limit of FeO in the liquid iron at the solidification temperature. The MgO addition was sufficient to reduce the oxygen level to 1,700 ppm. The results also showed that the effects of increasing oxidizing potential of the electrode covering on weld metal composition and microstructure are similar to those of increasing water depth. This finding is very significant since it allows for the simulation of deep water weld metal microstructures in shallow waters by controlling the oxidizing potential of the consumables used. Finally, studying the properties of oxidizing electrodes in shallow depths will also be useful in developing welding electrodes for deep waters.

  13. 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.

  14. 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. (National Heart, Lung, and Blood Institute, Bethesda, MD (USA))

    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.

  15. Chemical Looping Combustion - Reduction of nickel oxide\\/nickel aluminate with hydrogen

    Microsoft Academic Search

    Niklas Olsen

    Chemical Looping Combustion (CLC) has been proposed as a power\\/heat generating process with inherent CO2 separation, as the fuel is not combusted in direct contact with nitrogen in the air. In CLC the combustion of fossil fuels is split into separate oxidation and reduction reactions. A reducible metal oxide is cycled between the reactors, and acts as an oxygen carrier.

  16. 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...

  17. 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

  18. Bacterial reduction of crystalline Fe{sup 3+} oxides in single phase suspensions and subsurface materials

    Microsoft Academic Search

    John M. Zachara; JAMES K. FREDRICKSON; Shu-Mei W. Li; David W. Kennedy; Steven C. Smith; Paul L. Gassman

    1998-01-01

    Microbiologic reduction of synthetic and geologic Fe{sup 3+} oxides associated with four Pleistocene-age, Atlantic coastal plain sediments was investigated using a dissimilatory Fe reducing bacterium (Shewanella putrefaciens, strain CN32) in bicarbonate buffer. Experiments investigated whether phosphate and anthraquinone-2,6-disulfonate, (AQDS, a humic acid analogue) influenced the extent of crystalline Fe{sup 3+} oxide bioreduction and whether crystalline Fe{sup 3+} oxides in geologic

  19. 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.

  20. Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

    PubMed

    Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

    2015-05-26

    Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures. PMID:25844578

  1. Oxidation Reduction Potential of Complex Iron Compounds in Yeast

    Microsoft Academic Search

    Thomas B. Coolidge

    1931-01-01

    WHEN an alkaline extract of yeast is saturated with ammonium sulphate there is precipitated, with the protein, cytochrome `C' and a complex iron compound giving no visible spectrum. The latter can be separated from the proteins slowly by ultra-filtration. It remains in solution when the protein, with the cytochrome `C', is precipitated by trichloracetic acid.

  2. 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 [Toyota Central Research and Development Laboratories Inc., Nagakute, Aichi 480-1192 (Japan); Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma, Nara 630-0192 (Japan); Toyota Central Research and Development Laboratories Inc., Nagakute, Aichi 480-1192 (Japan); Ceramics Research Laboratory, Nagoya Institute of Technology, Tajimi, Gifu 507-0071 (Japan); Research and Education Center for Materials Science, Nara Institute of Science and Technology, Ikoma, Nara 630-0192 (Japan)

    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.

  3. MATHEMATICAL MODEL OF MOVING COKE BED FOR REDUCTION AND MELTING OF OXIDIZED IRON-SCRAP

    Microsoft Academic Search

    Xinghe Zhang; Hiroshi Nogami; Reijiro Takahashi; Jun-ichiro Yagi

    The reduction and melting of oxidized iron-scrap briquettes containing coke breeze in a moving bed reactor has been proposed from the viewpoints of energy saving, recycling and environmental protection. The aim of this study is to investigate the effect of the briquette on operation of the reduction-melting furnace. For this purpose, a total mathematical model of the reduction-melting furnace has

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  6. Mechanism of Potential Profile Formation in Silicon Single-Electron Transistors Fabricated Using Pattern-Dependent Oxidation

    Microsoft Academic Search

    Seiji Horiguchi; Masao Nagase; Kenji Shiraishi; Hiroyuki Kageshima; Yasuo Takahashi; Katsumi Murase

    2001-01-01

    The origin of the potential profile in silicon single-electron transistors (SETs) fabricated using pattern-dependent oxidation (PADOX) is investigated by making use of the geometric structure measured by atomic force microscope (AFM), the bandgap reduction due to compressive stress generated during PADOX obtained using the first-principles calculation, and the effective potential method. A probable mechanism for the formation of the potential

  7. Carbothermic reduction of uranium oxides into solvent metallic baths

    NASA Astrophysics Data System (ADS)

    Guisard Restivo, Thomaz A.; Capocchi, José D. T.

    2004-09-01

    The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

  8. 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.

  9. Chemical reduction of refractory oxides by atomic hydrogen

    Microsoft Academic Search

    D. Dooley; M. Balooch; D. R. Olander

    1978-01-01

    The chemical reduction of UO and AlO by atomic hydrogen was studied. Results of the UO\\/H investigation indicates that reduction of UO by atomic hydrogen proceeds by the production of water vapor and hypostoichiometric urania. Water vapor and aluminum metal are formed in the AlO\\/H system. The relative ease which UO is reduced by atomic hydrogen compared with AlO is

  10. Microbial reduction of manganese oxides: Interactions with iron and sulfur

    Microsoft Academic Search

    C. R. Myers; K. H. Nealson

    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{sup 3+} to Fe{sup 2+}, and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe{sup 2+} and sulfide act as rapid reductants of Mn. The addition of

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

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

    SciTech Connect

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

    2010-11-16

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

  13. Reduction

    NASA Astrophysics Data System (ADS)

    Cortez, Orfelinda Avalo; Moura, Francisco José; de Albuquerque Brocchi, Eduardo; de Siqueira, Rogério Navarro Correia; de Souza, Rodrigo Fernandes Magalhães

    2014-12-01

    Iron-nickel alloys have been synthesized through thermal decomposition of nitrates aqueous solutions followed by H2 reduction. The effect of temperature [773 K to 973 K (500 °C to 700 °C)] over the oxide reduction kinetics has been studied. The results indicate that at 973 K (700 °C) and for a reaction time of 90 minutes, it was possible to obtain Fe-Ni alloys with distinct compositions. The X-ray diffraction analysis (XRD) of the initial oxide mixture has shown distinct peaks of iron and nickel oxides (Fe2O3, NiO, and Fe2NiO4). The same analysis for the reduced samples suggests that alloying has taken place. Indeed, the Rietveld analysis of the XRD patterns indicates the presence of two solid solutions—alpha (BCC) and FeNi3 (FCC), with varying mass percent depending on the initial Fe to Ni ratio, in accordance with the information contained in the Fe-Ni phase diagram. The calculated alloy average crystallite size has shown to be equal to 26 nm. Total magnetization measurements suggest a superparamagnetic behavior, which is a typical result for magnetic materials of considerable nanostructured content, in accordance with the expectation based on the quantitative evaluation of the XRD data.

  14. 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.

  15. 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

  16. Oxygen diffusion at surface reduction in catalysts for selective oxidation

    Microsoft Academic Search

    O. Yu. Ovsitser; V. D. Sokolovskii

    1993-01-01

    The coefficient of oxygen diffusion and the activation energy for diffusion have been measured for the series of oxide catalysts of selective oxidation of organic compounds (Sm-Mg-O, Sm-O; V-P-O, Sn-Sb-O, Sn-Bi-O, Fe-Sb-O, Bi-Sb-O). The rates of oxygen diffusion under catalytic conditions have been compared with the reaction rates. For all studied systems (except Sm-O and Sm-Mg-O) at optimal operative temperatures

  17. 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.

  18. 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.

  19. Electric-field control of magnetism by reversible surface reduction and oxidation reactions

    NASA Astrophysics Data System (ADS)

    Leistner, K.; Wunderwald, J.; Lange, N.; Oswald, S.; Richter, M.; Zhang, H.; Schultz, L.; Fähler, S.

    2013-06-01

    Electric control of magnetism is a vision which drives intense research on magnetic semiconductors and multiferroics. Recently, ultrathin metallic films were also reported to show magnetoelectric effects at room temperature. Here we demonstrate much stronger effects by exploiting reduction/oxidation reactions in a naturally grown oxide layer exchange coupled to an underlying ferromagnet. For the exemplarily studied FePt/iron oxide composite in an electrolyte, a large and reversible change of magnetization and anisotropy is obtained. The principle can be transferred to various metal/oxide combinations. It represents an approach towards multifunctionality.

  20. 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

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

    PubMed Central

    2013-01-01

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

  2. Perchlorate reduction by a novel chemolithoautotrophic, hydrogen-oxidizing bacterium

    Microsoft Academic Search

    Husen Zhang; Mary Ann Bruns; Bruce E. Logan

    2002-01-01

    Summary Water treatment technologies are needed that can remove perchlorate from drinking water without introducing organic chemicals that stimulate bacterial growth in water distribution systems. Hydrogen is an ideal energy source for bacterial degradation of per- chlorate as it leaves no organic residue and is spar- ingly soluble. We describe here the isolation of a perchlorate-respiring, hydrogen-oxidizing bacterium ( Dechloromonas

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

    2014-10-01

    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.

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  6. Introduction The reduction of nitrogen oxide emissions is

    E-print Network

    Sandoghdar, Vahid

    combustors (such as gas-fired combustors,Figure 1) due to stringent emissions regulations. In Catalytically is attained in a post-catalyst homogeneous combustion zone.This process leads to substantial reduction of NOx emissions (typically NOx is produced exclusively from the gaseous (homogeneous) reaction path

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

    SciTech Connect

    Halder, S.; Fruehan, R.J. [Praxair Inc., Tonawanda, NY (United States). Technological Center

    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.

  8. 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.

  9. High rates of anaerobic methane oxidation in freshwater wetlands reduce potential atmospheric methane emissions.

    PubMed

    Segarra, K E A; Schubotz, F; Samarkin, V; Yoshinaga, M Y; Hinrichs, K-U; Joye, S B

    2015-01-01

    The role of anaerobic oxidation of methane (AOM) in wetlands, the largest natural source of atmospheric methane, is poorly constrained. Here we report rates of microbially mediated AOM (average rate=20?nmol?cm(-3) per day) in three freshwater wetlands that span multiple biogeographical provinces. The observed AOM rates rival those in marine environments. Most AOM activity may have been coupled to sulphate reduction, but other electron acceptors remain feasible. Lipid biomarkers typically associated with anaerobic methane-oxidizing archaea were more enriched in (13)C than those characteristic of marine systems, potentially due to distinct microbial metabolic pathways or dilution with heterotrophic isotope signals. On the basis of this extensive data set, AOM in freshwater wetlands may consume 200?Tg methane per year, reducing their potential methane emissions by over 50%. These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources. PMID:26123199

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

    SciTech Connect

    Roden, E.E.; Urrutia, M.M. [Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Biological Sciences] [Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Biological Sciences

    1999-06-01

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

  11. Nitrous Oxide Production and Reduction in the Sea Surface Microlayer: Nitrification or Denitrification?

    NASA Astrophysics Data System (ADS)

    Baggs, E. M.; Woo, J.

    2008-12-01

    Oceans are a significant source of atmospheric N2O, but may also act as a sink for both atmospheric and water column-derived N2O, mainly through reduction to N2 by denitrifying bacteria. The sea surface microlayer will play an important role in regulating the exchange of such greenhouse gases between the hydrosphere and the atmosphere, particularly as biological activity and bacterial abundance at this interface are greater than in the bulk water. Despite this, little is known of the role of the sea surface microlayer in ocean-atmosphere trace gas exchange. Here we adopted a stable isotope (15N-enrichment) approach to source partition this N2O between nitrification (ammonia oxidation) and denitrification throughout an artificial phytoplankton bloom. Water was sampled from the Raunefjord, Norway, and 16 ìmol nitrate L-1 and 1 ìmol phosphate L-1 were added to stimulate the bloom. We then applied a further 2 mM N as either 14NH415NO3 or 15NH415NO3 (10 atom percent excess 15N), to partition the measured 15N-N2O and 15N-N2 between nitrification and denitrification over a 7 day period. Following shaking, gases were sampled from the headspace and analysed for the 15N-enrichment of N2O and N2 by mass spectrometry. Here we discuss results in relation to the potential for N2O reduction to N2 within the sea surface microlayer, and the possible role of phytoplankton C in driving this reduction.

  12. Mechanisms of the hydrogen reduction of molybdenum oxides

    Microsoft Academic Search

    Werner V. Schulmeyer; Hugo M. Ortner

    2002-01-01

    The two stages of the hydrogen reduction of MoO3 to Mo were investigated in a thermal balance under well defined reaction conditions. Starting with different grain and agglomerate sizes for both stages, the influence of a set of parameters (temperature, local partial pressure of H2O, gas flow, etc.) on the reaction progress and the final result were studied in detail.

  13. 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.

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

    PubMed

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

    2015-05-14

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt. PMID:25978907

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  16. Kinetics of the reduction-oxidation processes taking place during the heating of powders produced from cast iron swarf

    Microsoft Academic Search

    S. S. Kiparisov; O. V. Padalko; E. S. Bogodukhova; L. A. Pronin; A. S. Mints

    1988-01-01

    An investigation was carried out, using the methods of gravimetric and chromatographic analyses, into the kinetics of the reduction-oxidation annealing (self-annealing) of cast iron swarf powders in an inert atmosphere. Reduction-oxidation was found to occur in two stages, in the temperature ranges 798–1163 and 1163–1523°K, respectively. The dominant process in the first stage was reduction of oxides by combined carbon,

  17. Enhancement of the reductive transformation of pentachlorophenol by polycarboxylic acids at the iron oxide-water interface.

    PubMed

    Li, Fangbai; Wang, Xugang; Li, Yongtao; Liu, Chengshuai; Zeng, Fang; Zhang, Lijia; Hao, Mingde; Ruan, Huada

    2008-05-15

    The enhancement effect of polycarboxylic acids on reductive dechlorination transformation of pentachlorophenol (PCP) reacting with iron oxides was studied in anoxic suspension. Batch experiments were performed with three species of iron oxides (goethite, lepidocrocite and hematite) and four species of polycarboxylic acids (oxalate, citrate, succinate, and tartrate) through anoxic abiotic reactors. The chemical analyses and morphological observation from scanning and transmission electron microscopy showed that different combinations between polycarboxylic acids and iron oxides produced distinct contents of Fe(II)-polycarboxylic ligand complexes, which significantly enhanced PCP transformation. Generation of the surface-bound Fe(II) depended on concentration of polycarboxylic acids. The optimal concentration for the enhancement was 2.0 mM oxalic acid. The dechlorination mechanism was further demonstrated by generation of chloride ions. The results suggest that surface-bound Fe(II) formed on the iron oxides surface appears to be a key factor in enhancing PCP transformation, and the mole ratio of oxalate to surface-bound Fe(II) (oxalate/Fe(II)) acted as an indicator of the enhancement effect. The enhancement mechanism attributes to strong nucleophilic ability and low reductive potential of the equivalent Fe(II)-polycarboxylate complexes. Therefore, the enhancement effects might be helpful for understanding the natural attenuation of reducible organic pollutants at the interface of contaminated soil in anoxic condition. PMID:18329661

  18. 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.

  19. TiO2-graphene nanocomposites. UV-assisted photocatalytic reduction of graphene oxide.

    PubMed

    Williams, Graeme; Seger, Brian; Kamat, Prashant V

    2008-07-01

    Graphene oxide suspended in ethanol undergoes reduction as it accepts electrons from UV-irradiated TiO(2) suspensions. The reduction is accompanied by changes in the absorption of the graphene oxide, as the color of the suspension shifts from brown to black. The direct interaction between TiO(2) particles and graphene sheets hinders the collapse of exfoliated sheets of graphene. Solid films cast on a borosilicate glass gap separated by gold-sputtered terminations show an order of magnitude decrease in lateral resistance following reduction with the TiO(2) photocatalyst. The photocatalytic methodology not only provides an on-demand UV-assisted reduction technique but also opens up new ways to obtain photoactive graphene-semiconductor composites. PMID:19206319

  20. Reductive Dissolution of Biogenic Manganese Oxides in the Presence of a Hydrated Biofilm

    Microsoft Academic Search

    Brandy Toner; Garrison Sposito

    2005-01-01

    The chemical reactivity of the biogenic Mn oxide produced by Pseudomonas putida strain MnB1 was assessed in the presence of bacterial cells and biofilm through reductive dissolution experiments at pH 4.4, 5.2, and 6.0. The reactivity of the biogenic Mn oxide was compared to that of a synthetic (chemically produced) birnessite at pH 6.0. In addition, the effect of bacterial

  1. Contribution of oxidative-reductive reactions to high-molecular-weight hyaluronan catabolism.

    PubMed

    Soltés, Ladislav; Stankovská, Monika; Kogan, Grigorij; Gemeiner, Peter; Stern, Robert

    2005-09-01

    Since the content of hyaluronan (HA)-degrading enzymes in synovial fluid (SF), if any, is extremely low, the high rate of HA turnover in SF is to result from a cause different from enzymatic catabolism. An alternative and plausible mechanism is that of oxidative-reductive degradation of HA chains by a combined action of oxygen and transition metal cations maintained in a reduced oxidation state by ascorbate. PMID:17193206

  2. Reduction of graphene oxide monolayers transferred on Si and Ti substrates by LB technique

    NASA Astrophysics Data System (ADS)

    Singh, Gulbagh; Botcha, V. Divakar; Narayanam, Pavan K.; Sutar, D. S.; Talwar, S. S.; Srinivasa, R. S.; Major, S. S.

    2012-06-01

    Graphene oxide sheets were transferred on Si and Ti substrates by Langmuir-Blodgett technique and were reduced by hydrazine vapor treatment followed by annealing in vacuum/inert atmosphere. A comparison of Raman spectra of reduced graphene oxide on Si and Ti shows that the reduction process is more effective in the later case and results in the formation of RGO with higher graphitic carbon content, exhibiting spectral features closer to those of graphene monolayers.

  3. Reduction of copper oxides by UV radiation and atomic hydrogen studied by XPS

    NASA Astrophysics Data System (ADS)

    Fleisch, T. H.; Mains, G. J.

    The reduction of polycrystalline cupric oxide (CuO) and cuprous oxide (Cu 2O) by UV irradiation and by atomic hydrogen was investigated with X-ray photoelectron spectroscopy (XPS or ESCA). UV photons from a low pressure mercury lamp(?=2537A, hv=4.8cV) slowly reduce both CuO and Cu 2O at room temperature. After approximately 10 h of irradiation the sample surfaces appear completely reduced to metallic Cu. This indicates that after that time the top 30 A of the sample pellets, the approximate sampling depth of XPS, have been reduced. Further irradiation causes the reduction to progress through the pellet interior and bulk phase. The sample color changes from dark to metallic copper. Photochemically generated hydrogen atoms reduce copper oxides at ambient temperatures. The reduction rate is about 10 times faster than the one caused by UV light alone. The reduction of Cu 2O is in both cases slightly slower than the one of CuO. The degree of reduction has been calculated from XPS data in different ways involving the atomic ratio of O/Cu, the relative intensity of the shake-up structure of CuO, and changes in the structure of the Cu L 3M 45M 45 Auger line. Freshly reduced Cu surfaces are sensitive to air exposure. They oxidize easily to Cu 2O.

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

    SciTech Connect

    Gardner, S.D.; Hoflund, G.B.; Davidson, M.R. (Univ. of Florida, Gainesville (USA)); Schryer, D.R. (NASA Langley Research Center, Hampton, VA (USA))

    1989-01-01

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

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

    Microsoft Academic Search

    Eric E. Roden; Matilde M. Urrutia

    1999-01-01

    Semicontinuous cultures were used to assess the effect of aqueous Fe(II) removal on the dissimilatory reduction of crystalline Fe(III) oxides by Shewanella alga strain BrY. Aqueous phase replacement in semicontinuous cultures resulted in a 2--3-fold increase in the cumulative amount of Fe(II) produced from synthetic goethite reduction over a 2-month incubation period, compared to parallel batch cultures. A more modest

  6. POTENTIALLY GOOD REDUCTION OF BARSOTTI-TATE GROUPS ...

    E-print Network

    2006-04-10

    TONG LIU. Abstract. Let R be a complete discrete valuation ring of mixed character- ... reduction over a finite extension K of K. We prove that there exists a con- ... be generalized to study semi-stable p-adic Galois representations with gen- .... a short exact sequence of finite free R -modules with semi-linear ?-

  7. 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.

  8. Potential Distribution and Negative Resistance in Thin Oxide Films

    Microsoft Academic Search

    T. W. Hickmott

    1964-01-01

    Al&sngbnd;SiO&sngbnd;Al&sngbnd;SiO&sngbnd;Au triodes with SiO thicknesses between 150 and 500 Å have been used to measure the potential distribution in thin oxide films before, during, and after the development of voltage-controlled negative resistance (VCNR) in the current-voltage characteristics. Development of VCNR in the triode is accompanied by the establishment of a high-field region about 120 Å in thickness near the negative

  9. Reduction of carbon monoxide emissions with regenerative thermal oxidizers

    SciTech Connect

    Firmin, S.M.; Lipke, S.; Baturay, A.

    1996-09-01

    Regenerative thermal oxidizers (RTOs) have been extensively used for the control of volatile organic compound (VOC) emissions from various sources. However, very little information is available on the ability of RTOs to control carbon monoxide (CO) emissions. This paper presents the results of extensive tests conducted on two RTOs to determine their VOC and CO control efficiencies. The inlet gas stream to the RTOs includes VOC and CO concentrations as high as 2,000 ppm and 3,600 ppm, respectfully. The testing demonstrated that both RTOs were capable of controlling greater than 98% of both inlet VOCs and CO. While the destruction efficiencies within the combustion chambers exceeded 99.9%, direct leakage past valves accounted for the lower control efficiencies. The tests indicated that the overall VOC and CO control efficiencies of the RTOs may be limited by valve leakage. The design and permitting of a RTO should include conservative control estimates which account for possible valve leakage.

  10. Options for VOC reduction in a regenerative thermal oxidizer (RTO)

    SciTech Connect

    Waldern, P.J.; Nutcher, P.; Lewandowski, D. [Process Combustion Corp. (PCC), Pittsburgh, PA (United States)

    1997-12-31

    Environmental regulations stemming from the 1990 Clean Air Act amendments are requiring treatment of high volume but relatively dilute VOC contaminated air and waste gas streams. Because of its low operating costs, Regenerative Thermal Oxidation (RTO) has emerged as the preferred treatment method for many of these streams. In the past, this technology usually required multiple (3 or more) beds of heat sink packing. However, some new units are being supplied with only two beds. Consequently, capital costs are lower. This paper describes test data from a unique twin bed RTO. Data for two different types of heat sink material will be presented, random packing and structured packing. The effect of cycle time, bed length, and packing type on thermal efficiency will be described. A cost comparison is included showing the effect of packing type on both capital and operating costs for various RTO sizes.

  11. The low-temperature reduction of Pd-doped transition metal oxide surfaces with hydrogen

    Microsoft Academic Search

    V. M. Belousov; M. A. Vasylyev; L. V. Lyashenko; N. Yu. Vilkova; B. E. Nieuwenhuys

    2003-01-01

    The reaction of hydrogen with a series of polyvalent metal oxides (Fe2O3, WO3, MoO3, V2O5, Sb2O3, PbO2, Cr2O3, NiO, CuO, Co3O4, MnO2, PdO, Ag2O) was investigated at low temperatures (77–320K) and pressures (0.001–0.7kPa). Pd-doped (0.1–0.5wt.%) transition metal oxides can be reduced by hydrogen at 77–320K whereas the onset of the reduction of the pure oxides occurs at temperatures higher than

  12. Potential-modulated reflectance study of the oxidation state of iridium in anodic iridium oxide films

    SciTech Connect

    Gutierrez, C.; Sanchez, M.; Pena, J.I.; Martinez, C.; Martinez, M.A.

    1987-09-01

    In an attempt to identify the changes of oxidation state involved in the electrochromic effect of anodic iridium oxide films (AIROF's) the authors obtained potential-modulated reflectance (PMR) spectra of AIROF's at three pH values: 0.9, 6.7, and 13.0, in the wavelength range 200-650 nm and at an angle of incidence of 45/sup 0/. Depending on pH, the voltammograms show up to four peaks (I-IV) in the anodic scan, the coloration-bleaching process corresponding to the main voltammetric peak II. The PMR spectra measured at a given voltammetric feature were nearly independent of pH, which shows that (i) the chemical composition of the AIROF is largely independent of the pH of the solution in which it was grown; (ii) the reflectance signal is originated by changes of the oxidation state of iridium in the AIROF. The PMR spectra were independent of the thickness of the AIROF, and therefore were not a trivial interference effect. The PMR maximum at 580-610 nm at voltammetric peak II has been tentatively assigned to an Ir(IV) oxide or oxyhydroxide, as have the PMR maximum at 330-360 nm at the minimum between voltammetric peaks II and III and the PMR maximum at 220-260 nm at potentials at or above voltammetric peak III. Apparently an Ir(IV) oxide or oxyhydroxide predominates in the potential range between voltammetric peaks II and IV, and different transitions become possible in this oxide at increasingly positive potentials.

  13. Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.

    PubMed

    Luo, Yun; Habrioux, Aurélien; Calvillo, Laura; Granozzi, Gaetano; Alonso-Vante, Nicolas

    2014-07-21

    Rare-earth-element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC-72) are synthesized via a water-in-oil chemical route. In both cases, X-ray diffraction (XRD) measurements show the non-formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt-Y(2)O(3) and Pt-Gd(2)O(3) particles are well dispersed on the substrate-and that their average particle sizes are smaller than the Pt-NP sizes. The catalytic activity of the Pt-Y(2)O(3)/C and Pt-Gd(2)O(3)/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5?M H(2)SO(4) electrolyte. The surface and mass specific activities of the Pt-Y(2)O(3)/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) ?A?cm(-2)(Pt) and MA=(23.1±0.5) mA?mg(-1)(Pt), respectively. These values are 1.3-, and 1.6-fold higher than the values obtained with a Pt/C catalyst. Although the as-prepared Pt-Gd(2)O(3)/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat-treated sample shows a surface specific activity of about (53.0±0.7) ?A?cm(-2) Pt , and a mass specific activity (MA) of about (18.2±0.5) mA?mg(-1) Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt-Y(2)O(3)/C and heat-treated Pt-Gd(2)O(3)/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties. PMID:24819164

  14. Characterization study of polycrystalline tin oxide surfaces before and after reduction in CO

    NASA Technical Reports Server (NTRS)

    Drawdy, Jean E.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

    1990-01-01

    Polycrystalline tin oxide surfaces have been examined before and after reduction in 40 Torr of CO at 100 and 175 C using Auger electron spectroscopy (AES), electron spectroscopy for chemical analysis (ESCA), ion scattering spectroscopy (ISS) and electron stimulated desorption (ESD). The changes in the surface composition and chemical states of the surface species generally are subtle for the reductive conditions used. However, significant changes do occur with regard to the amounts and the chemical forms of the hydrogen-containing species remaining after both the 100 and 175 C reductions.

  15. 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. ...

  16. Synthesis of reduced graphene oxide (rGO) via chemical reduction

    NASA Astrophysics Data System (ADS)

    Thakur, Alpana; Kumar, Sunil; Rangra, V. S.

    2015-05-01

    Natural flake Graphite was used as the starting material for the graphene synthesis. In the first step flake graphite was treated with oxidizing agents under vigorous conditions to obtain graphite oxide. Layered graphite oxide decorated with oxygen has large inter-layer distance leading easy exfoliation into single sheets by ultrasonication giving graphene oxide. In the last step exfoliated graphene oxide sheets were reduced slowly with the help of reducing agent to obtain fine powder which is labeled as reduced graphene oxide (rGO). This rGO was further characterized by X-Ray Diffraction (XRD), Scanning Tunneling Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy techniques. XRD pattern shows peaks corresponding to (002) graphitic lattice planes indicating the formation of network of sp2 like carbon structure. SEM images show the ultrathin, wrinkled, paper-like morphology of graphene sheets. IR study shows that the graphite has been oxidized to graphite oxide with the presence of various absorption bands confirming the presence of oxidizing groups. The FTIR spectrum of rGO shows no sharp peaks confirming the efficient reduction of rGO. The Raman spectrum shows disorder in the graphene sheets.

  17. Explosive thermal reduction of graphene oxide-based materials: mechanism and safety implications.

    PubMed

    Qiu, Yang; Guo, Fei; Hurt, Robert; Külaots, Indrek

    2014-06-01

    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 m(2)g(-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

  18. 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

  19. 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.

  20. Intracellular Oxidation-Reduction State Measured in situ by a Multichannel Fiber-Optic Surface Fluorometer

    Microsoft Academic Search

    Avraham Mayevsky; Britton Chance

    1982-01-01

    The principles of the measurement in vivo of the oxidation-reduction state of intramitochrondrial pyridine nucleotides were used in establishing a multichannel fluorometer-reflectometer. This approach made possible the study of changes of mitochrondrial redox states in four different organs (brain, liver, kidney, and testis) of the same animal, as well as the monitoring of four different cortical areas of the same

  1. 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…

  2. Production of N2 through Anaerobic Ammonium Oxidation Coupled to Nitrate Reduction in Marine Sediments

    Microsoft Academic Search

    Bo Thamdrup; Tage Dalsgaard

    2002-01-01

    In the global nitrogen cycle, bacterial denitrification is recognized as the only quantitatively important process that converts fixed nitrogen to atmospheric nitrogen gas, N2, thereby influencing many aspects of ecosystem function and global biogeochemistry. However, we have found that a process novel to the marine nitrogen cycle, anaerobic oxidation of ammonium coupled to nitrate reduction, contributes substantially to N2 production

  3. Advanced Experiment Analysis of controls on Microbial FE(III) Oxide Reduction

    SciTech Connect

    Roden, Eric E.; Urrutia, Matilde M.

    1999-06-01

    Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting the ability of these organisms to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine our quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction activity.

  4. 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...

  5. Structure Sensitivity of Photochemical Oxidation and Reduction Reactions on SrTiO3 Surfaces

    E-print Network

    Rohrer, Gregory S.

    Structure Sensitivity of Photochemical Oxidation and Reduction Reactions on SrTiO3 Surfaces) on the surface. Mi- croscopic analysis has been used to relate the rates of these two reactions to the structure and the composition of the termination layer does not influence this reaction. On the polar (111) surface

  6. The mechanism of the selective reduction of nitrogen oxides by hydrocarbons on zeolite catalysts

    Microsoft Academic Search

    Noel W. Cant; Irene O. Y. Liu

    2000-01-01

    The mechanism of the selective catalytic reduction (SCR) of nitrogen oxides over 3d transition metal zeolites has been investigated in a variety of ways. The initial step is the abstraction of hydrogen from the hydrocarbon by adsorbed NO2 species which is rate determining with methane but not with isobutane. The subsequent path appears to involve nitroso and\\/or nitro compounds. Comparative

  7. 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...

  8. 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.

  9. Nitric oxide from nitrite reduction by hemoglobin in the plasma and erythrocytes

    E-print Network

    Popel, Aleksander S.

    Nitric oxide from nitrite reduction by hemoglobin in the plasma and erythrocytes Kejing Chen a the erythrocyte acts as a NO generator and deoxygenated hemoglobin in pre-capillary arterioles reduces nitrite the model. Our calculations show that: (1) $0.04 pM NO from erythrocytes could reach the smooth muscle

  10. Reduction and oxidation of peptide nucleic acid and DNA at mercury and carbon electrodes

    Microsoft Academic Search

    Miroslav Tomschik; František Jelen; Lud?k Havran; Libuše Trnková; Peter E Nielsen; Emil Pale?ek

    1999-01-01

    Peptide nucleic acid (PNA) is a DNA mimic that binds strongly and specifically to complementary DNA or RNA oligomers, but in contrast to DNA its backbone does not carry any electric charge. We used voltammetry in cyclic and square-wave modes to study reduction and oxidation signals of single stranded (ss)PNA and DNA decamers and pentadecamers with the same base sequences

  11. THE REDUCTION OF POTENTIAL DIFFUSIONS TO FINITE STATE

    E-print Network

    Imkeller, Peter

    , periodicity of trajectories has to be studied by means of a measure of quality of tuning such as spectral, spectral gap, stochastic di#11;erential equation, en- ergy balance model, potential di#11;usion, e#11

  12. Potential CO2 Emission Reduction by Development of Non-Grain-Based Bioethanol in China

    NASA Astrophysics Data System (ADS)

    Li, Hongqiang; Wang, Limao; Shen, Lei

    2010-10-01

    Assessment of the potential CO2 emission reduction by development of non-grain-based ethanol in China is valuable for both setting up countermeasures against climate change and formulating bioethanol policies. Based on the land occupation property, feedstock classification and selection are conducted, identifying sweet sorghum, cassava, and sweet potato as plantation feedstocks cultivated from low-quality arable marginal land resources and molasses and agricultural straws as nonplantation feedstocks derived from agricultural by-products. The feedstock utilization degree, CO2 reduction coefficient of bioethanol, and assessment model of CO2 emission reduction potential of bioethanol are proposed and established to assess the potential CO2 emission reduction by development of non-grain-based bioethanol. The results show that China can obtain emission reduction potentials of 10.947 and 49.027 Mt CO2 with non-grain-based bioethanol in 2015 and 2030, which are much higher than the present capacity, calculated as 1.95 Mt. It is found that nonplantation feedstock can produce more bioethanol so as to obtain a higher potential than plantation feedstock in both 2015 and 2030. Another finding is that developing non-grain-based bioethanol can make only a limited contribution to China’s greenhouse gas emission reduction. Moreover, this study reveals that the regions with low and very low potentials for emission reduction will dominate the spatial distribution in 2015, and regions with high and very high potentials will be the majority in 2030.

  13. Intermolecular potential energy surface and thermophysical properties of ethylene oxide

    NASA Astrophysics Data System (ADS)

    Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

    2014-10-01

    A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

  14. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    SciTech Connect

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

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and pattern of FeRB growth with different Fe(III) forms, a roughly consistent long-term biomass yield of 5 to 15 mg protein per mmol Fe(III) reduced was observed during growth on different forms of Fe(III). These results should prove useful for quantitative modeling of FeRB growth and metabolism in various types of experimental and in situ anaerobic sedimentary systems.'

  15. Reduction phases of thin iron-oxide nanowires upon thermal treatment and Li exposure

    NASA Astrophysics Data System (ADS)

    Angelucci, Marco; Frau, Eleonora; Hassoun, Jusef; Hong, Inchul; Grazia Betti, Maria; Panero, Stefania; Scrosati, Bruno; Mariani, Carlo

    2014-04-01

    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 Fe2O3 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 Fe3O4 and then to a Fe2+ phase, as determined by means of core-level photoemission spectroscopy. Mild annealing of Fe2O3 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.

  16. 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

  17. 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

  18. Bacterial reduction of crystalline Fe{sup 3+} oxides in single phase suspensions and subsurface materials

    SciTech Connect

    Zachara, J.M.; Fredrickson, J.K.; Li, S.M.; Kennedy, D.W.; Smith, S.C.; Gassman, P.L. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-11-01

    Microbiologic reduction of synthetic and geologic Fe{sup 3+} oxides associated with four Pleistocene-age, Atlantic coastal plain sediments was investigated using a dissimilatory Fe reducing bacterium (Shewanella putrefaciens, strain CN32) in bicarbonate buffer. Experiments investigated whether phosphate and anthraquinone-2,6-disulfonate, (AQDS, a humic acid analogue) influenced the extent of crystalline Fe{sup 3+} oxide bioreduction and whether crystalline Fe{sup 3+} oxides in geologic materials are more or less reducible than comparable synthetic phases. Anaerobic incubations (10{sup 8} organisms/mL) were performed both with and without PO{sub 4} and AQDS that functions as an electron repository and shuttle. The production of Fe{sup 2+} (solid and aqueous) was followed with time, as was mineralogy by X-ray diffraction. The synthetic oxides were reduced in a qualitative trend consistent with their surface area and free energy: hydrous ferric oxide (HFO) > goethite > hematite. Bacterial reduction of the crystalline oxides was incomplete in spite of excess electron donor. Biogenic formation of vivianite [Fe{sub 3}(PO{sub 4}){sub 2}{center_dot}8H{sub 2}O] and siderite (FeCO{sub 3}) was observed; the conditions of their formation was consistent with their solubility. The geologic Fe{sup 3+} oxides showed a large range in reducibility, approaching 100% in some materials. The natural oxides were equally or more reducible than their synthetic counterparts, in spite of association with non-reducible mineral phases (e.g., kaolinite). The reducibility of the synthetic and geologic oxides was weakly effected by PO{sub 4}, but was accelerated by AQDS. CN32 produced the hydroquinone form of AQDS (AHDS), that, in turn, had thermodynamic power to reduce the Fe{sup 3+} oxides. As a chemical reductant, it could reach physical regions of the oxide not accessible by the organism. Electron microscopy showed that crystallite size was not the primary factor that caused differences in reducibility between natural and synthetic crystalline Fe{sup 3+} oxide phases. Crystalline disorder and microheterogeneities may be more important.

  19. Reduction of graphene oxide by aniline with its concomitant oxidative polymerization.

    PubMed

    Xu, Li Qun; Liu, Yi Liang; Neoh, Koon-Gee; Kang, En-Tang; Fu, Guo Dong

    2011-04-19

    Graphene oxide (GO) nanosheets are readily reduced by aniline above room temperature in an aqueous acid medium, with the aniline simultaneously undergoing oxidative polymerization to produce the reduced graphene oxide-polyaniline nanofiber (RGO-PANi) composites. The resulting RGO-PANi composites and RGO (after dissolution of PANi) were characterized by XPS, XRD analysis, TGA, UV-visible absorption spectroscopy, and TEM. It was also found that the RGO-PANi composites exhibit good specific capacitance during galvanostatic charging-discharging when used as capacitor electrodes. PMID:21480428

  20. Palladium and gold nanotubes as oxygen reduction reaction and alcohol oxidation reaction catalysts in base.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2014-06-01

    Palladium (PdNTs) and gold nanotubes (AuNTs) were synthesized by the galvanic displacement of silver nanowires. PdNTs and AuNTs have wall thicknesses of 6?nm, outer diameters of 60?nm, and lengths of 5-10 and 5-20??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

  1. Electrocatalytic reduction of nitrite and nitric oxide to ammonia with iron-substituted polyoxotungstates

    SciTech Connect

    Toth, J.E.; Anson, F.C. (California Institute of Technology, Pasadena (USA))

    1989-03-29

    Heteropolytungstates in which one of the positions normally occupied by a tungsten cation is occupied instead by an iron cation are shown to be catalysts for the electroreduction of nitrite to ammonia. The lacunary derivatives in which the empty tungsten site is unoccupied show no catalytic activity. The catalytic mechanism involves the intermediate formation of a nitrosyl complex of the Fe(II) form of the catalyst. The pH dependence of the rate of formation of the nitrosyl complex shows that nitrous acid is the reactive form of nitrite between pH 2 and 8. The catalyzed reduction does not produce hydroxylamine as an intermediate and appears to depend upon the ability of the multiply reduced heteropolytungstates to deliver electrons to the NO group bound to the iron center in a concerted, multiple-electron step. The iron-substituted heteropolytungstates are not degraded by repeated cycling between their oxidized and reduced states. A particularly valuable feature of the heteropolytungstate is the ease with which the formal potentials of the several redox couples they exhibit may be shifted by changing the identity of the central heteroatom. Exploitation of this feature provides diagnostic information that can be decisive in establishing the mechanism of electrocatalytic processes.

  2. One-step reduction and PEGylation of graphene oxide for photothermally controlled drug delivery.

    PubMed

    Chen, Jingqin; Liu, Hongyu; Zhao, Chubiao; Qin, Guiqi; Xi, Gaina; Li, Tan; Wang, Xiaoping; Chen, Tongsheng

    2014-06-01

    Here, we developed one-step green reduction and PEGylation of nanosized graphene oxide (NGO) to obtain NrGO/PEG as a photothermally controllable drug delivery system. NrGO/PEG was synthesized by bathing methoxypolyethylene glycol amine (mPEG-NH2) and NGO at 90 °C for 24 h. The NrGO/PEG kept water stability for at least two months, and had ~14-fold increment in near-infrared (NIR) absorbance and ~2-fold increment in resveratrol (RV) loading over the unreduced NGO/PEG via ?-? and hydrophobic interactions. Exposure of 4T1 cells to NrGO/PEG for 2 h showed 53.6% uptake ratio, and localization of NrGO/PEG in lysosomes instead of mitochondria. NIR irradiation (808 nm laser at 0.6 W/cm(2)) for 3 min potently enhanced RV release from NrGO/PEG-RV and the cytotoxicity of NrGO/PEG-RV against 4T1 cells, including decrease of cell viability, loss of mitochondrial membrane potential (??m) and cell apoptosis. Finally, NIR irradiation dramatically enhanced the efficacy of NrGO/PEG-RV in suppressing tumor growth in animal tumor models, further proving the remarkable synergistic action between photothermal effect of NrGO/PEG and RV loaded on NrGO/PEG. PMID:24656608

  3. Polydopamine-graphene oxide derived mesoporous carbon nanosheets for enhanced oxygen reduction.

    PubMed

    Qu, Konggang; Zheng, Yao; Dai, Sheng; Qiao, Shi Zhang

    2015-08-01

    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. PMID:26147787

  4. Control of combustion-generated nitrogen oxides by selective non-catalytic reduction.

    PubMed

    Javed, M Tayyeb; Irfan, Naseem; Gibbs, B M

    2007-05-01

    Controlling nitrogen oxides (NO(x)) emissions is becoming a daunting technical challenge as increasingly strict emission limits are being imposed. The stringent regulations have prompted the innovation and characterization of NO(x) control technologies suitable for various applications. This paper presents a review on NO(x) removal techniques with particular reference to selective non-catalytic reduction (SNCR) technology. This includes initially how SNCR emerged as a technology along with a comparison with other relevant technologies. A review of various features related to selective non-catalytic gas phase injection of ammonia and ammonium salts (as reducing agent) is presented. The use of urea solution as a reducing agent and its performance in laboratory and pilot scale tests as well as large-scale applications is also discussed. Use of cyanuric acid as a potential reducing agent is also presented. The underlying reaction mechanisms have been reviewed for ammonia, urea and cyanuric acid for the explanation of various observations. Computational fluid dynamics (CFD) modeling as applied to SNCR is also presented. Subsequently the use of SNCR coupled with other in-combustion and post-combustion NO(x) control techniques is elaborated. Additionally, a two-stage NO(x) removal strategy to control un-reacted ammonia slip and to improve overall efficiency is discussed. At the end a summary is given which highlights various areas needing further research. PMID:16842901

  5. Wet air oxidation pretreatment of biomethanated distillery effluent: mapping pretreatment efficiency in terms color, toxicity reduction and biogas generation.

    PubMed

    Sarat Chandra, T; Malik, S N; Suvidha, G; Padmere, M L; Shanmugam, P; Mudliar, S N

    2014-04-01

    The effluents from molasses-based distilleries after biomethanation are beset with problems of intensified dark brown color, high residual COD, low biodegradability index (BOD/COD ratio <0.2) and toxicity issues for possible land application as a potential fertilizer. Wet air oxidation (WAO) pretreatment of biomethanated distillery effluent resulted in substantial enhancement in the biodegradability index (BI) (up to 0.8). WAO pretreated effluent on anaerobic digestion indicated favorable biogas generation with methane content up to 64% along with concomitant COD reduction up to 54.75%. The HPLC analysis indicated that the pretreatment facilitated degradation of major color containing compounds-namely melanoidins, up to 97.8%. The pretreated effluent with enhanced biodegradability along with substantially reduced color also indicated positive effect on seed germination (up to 100%), implying toxicity reduction of the effluent post WAO pretreatment. PMID:24583914

  6. Protein-bound acrolein: Potential markers for oxidative stress

    PubMed Central

    Uchida, Koji; Kanematsu, Masamichi; Sakai, Kensuke; Matsuda, Tsukasa; Hattori, Nobutaka; Mizuno, Yoshikuni; Suzuki, Daisuke; Miyata, Toshio; Noguchi, Noriko; Niki, Etsuo; Osawa, Toshihiko

    1998-01-01

    Acrolein (CH2=CH—CHO) is known as a ubiquitous pollutant in the environment. Here we show that this notorious aldehyde is not just a pollutant, but also a lipid peroxidation product that could be ubiquitously generated in biological systems. Upon incubation with BSA, acrolein was rapidly incorporated into the protein and generated the protein-linked carbonyl derivative, a putative marker of oxidatively modified proteins under oxidative stress. To verify the presence of protein-bound acrolein in vivo, the mAb (mAb5F6) against the acrolein-modified keyhole limpet hemocyanin was raised. It was found that the acrolein-lysine adduct, N?-(3-formyl-3,4-dehydropiperidino)lysine, constitutes an epitope of the antibody. Immunohistochemical analysis of atherosclerotic lesions from a human aorta demonstrated that antigenic materials recognized by mAb5F6 indeed constituted the lesions, in which intense positivity was associated primarily with macrophage-derived foam cells and the thickening neointima of arterial walls. The observations that (i) oxidative modification of low-density lipoprotein with Cu2+ generated the acrolein-low-density lipoprotein adducts and (ii) the iron-catalyzed oxidation of arachidonate in the presence of protein resulted in the formation of antigenic materials suggested that polyunsaturated fatty acids are sources of acrolein that cause the production of protein-bound acrolein. These data suggest that the protein-bound acrolein represents potential markers of oxidative stress and long-term damage to protein in aging, atherosclerosis, and diabetes. PMID:9560197

  7. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    USGS Publications Warehouse

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

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  8. Biogenic metals for the oxidative and reductive removal of pharmaceuticals, biocides and iodinated contrast media in a polishing membrane bioreactor.

    PubMed

    Forrez, Ilse; Carballa, Marta; Fink, Guido; Wick, Arne; Hennebel, Tom; Vanhaecke, Lynn; Ternes, Thomas; Boon, Nico; Verstraete, Willy

    2011-02-01

    Pharmaceutical and personal care products, biocides and iodinated contrast media (ICM) are persistent compounds, which appear in ng to ?g L(-1) in secondary effluents of sewage treatment plants (STPs). In this work, biogenic metals manganese oxides (BioMnOx) and bio-palladium (Bio-Pd) were applied in lab-scale membrane bioreactors (MBR) as oxidative and reductive technologies, respectively, to remove micropollutants from STP-effluent. From the 29 substances detected in the STP-effluent, 14 were eliminated in the BioMnOx-MBR: ibuprofen (>95%), naproxen (>95%), diuron (>94%), codeine (>93%), N-acetyl-sulfamethoxazole (92%), chlorophene (>89%), diclofenac (86%), mecoprop (81%), triclosan (>78%), clarithromycin, (75%), iohexol (72%), iopromide (68%), iomeprol (63%) and sulfamethoxazole (52%). The putative removal mechanisms were the chemical oxidation by BioMnOx and/or the biological removal by Pseudomonas putida and associated bacteria in the enriched biofilm. Yet, the removal rates (highest value: 2.6 ?g diclofenac L(-1) d(-1)) need to improve by a factor 10 in order to be competitive with ozonation. ICM, persistent towards oxidative techniques, were successfully dehalogenated with a novel reductive technique using Bio-Pd as a nanosized catalyst in an MBR. Iomeprol, iopromide and iohexol were removed for >97% and the more recalcitrant diatrizoate for 90%. The conditions favorable for microbial H(2)-production enabling the charging of the Pd catalyst, were shown to be important for the removal of ICM. Overall, the results indicate that Mn oxide and Pd coupled to microbial catalysis offer novel potential for advanced water treatment. PMID:21163512

  9. 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 ...

  10. THE REDUCTION OF POTENTIAL DIFFUSIONS TO FINITE STATE

    E-print Network

    Pavlyukevich, Ilya

    , periodicity of trajectories has to be studied by means of a measure of quality of tuning such as spectral are carefully eliminated, the reduced dynamics is robust. Keywords: Stochastic resonance, spectral gap, stochastic differential equation, en- ergy balance model, potential diffusion, effective dynamics. 1 #12;2 1

  11. Potential of municipal solid waste for renewable energy production and reduction of greenhouse gas emissions in South Korea.

    PubMed

    Ryu, Changkook

    2010-02-01

    Energy from waste (EfW) for nonrecyclable wastes is a suitable method of waste management and is important for renewable energy production. South Korea currently recycles 57% of household waste and landfills 26%. The remaining 17% is incinerated, mainly for heat production. In this study, the potential for energy production and reduction of corresponding greenhouse gas (GHG) emissions from municipal solid waste (MSW) in Korea was estimated without accounting for the lifecycle impact of waste management. The properties of the MSW were established from data available in national-scale waste surveys and reports. The potential of EfW for GHG emission reduction was calculated considering (1) the direct release of anthropogenic carbon, nitrous oxide (N2O), and methane (CH4); and (2) the reduction in indirect GHG emissions by fossil fuel displacement. CH4 emissions from landfilling were also estimated from biogenic carbon in waste. Applying the resulting emission factors to various EfW cases suggests that the current level of GHG emissions is significant but can be substantially reduced by increased use of EfW. A net reduction in GHG emissions can be achieved only by EfW with combined heat and power (CHP). PMID:20222530

  12. Crystallographically aligned metal-oxide composite made by reduction of a directionally solidified oxide-oxide eutectic

    Microsoft Academic Search

    A. Revcolevschi; G. Dhalenne

    1985-01-01

    Aligned metal-oxide composite materials have been grown from the melt by directional solidification at eutectic composition of several binary metal-oxide systems. The resulting microstructures consist of metallic fibres ~1 µm in diameter imbedded in an oxide matrix1,2. The occurrence of such fibrous structures, as opposed to lamellar structures, corresponds to eutectic compositions for which the volume fraction of the minor

  13. Sildenafil potentiates nitric oxide mediated inhibition of human platelet aggregation

    Microsoft Academic Search

    Ingibjörg J. Gudmundsdóttir; Sarah J. McRobbie; Simon D. Robinson; David E. Newby; Ian L. Megson

    2005-01-01

    Nitric oxide (NO) inhibits platelet aggregation primarily via a cyclic 3?5?-guanosine monophosphate (cGMP)-dependent process. Sildenafil is a phosphodiesterase type 5 (PDE5) inhibitor that potentiates NO action by reducing cGMP breakdown. We hypothesised that sildenafil would augment the inhibitory effects of NO on in vitro platelet aggregation. After incubation with sildenafil or the soluble guanylate cyclase inhibitor H-(1,2,4)oxadiazolo(4,3-a)quinoxallin-1-one (ODQ), collagen-mediated human

  14. Measuring the Kinetics of the Reduction of Iron Oxide with Carbon Monoxide in a Fluidized Bed

    NASA Astrophysics Data System (ADS)

    Bohnt, C. D.; Cleeton, J. P.; Miiller, C. M.; Scotr, S. A.; Dennis, J. S.

    Combusting a solid fuel in the presence of a metal oxide rather than air, chemical looping combustion, generates CO2suitable for sequestration and the reduced metal. For the case of iron, the reduced oxide can be re-oxidized with steam to produce high-purity hydrogen. The reduction reactions of iron oxide in carbon monoxide and carbon dioxide mixtures were investigated in a fluidized bed. Activation energies and pre-exponential factors for the reactions (i) 3 Fe2O3+CO?2 Fe3O4+CO2 and?(ii)0.947 Fe3O4+0.788 CO?3 Fe0.947O+0.788 CO2?were determined. The reaction order was verified to be unity, and the change in rate with conversion was examined.

  15. Valence states of vanadia-on-titania\\/silica and molybdena-on-silica catalysts after reduction and oxidation

    Microsoft Academic Search

    J. J. P. Biermann; F. J. J. G. Janssen; J. R. H. Ross

    1990-01-01

    The behavior of vanadia-on-titania\\/silica and molybdena-on-silica catalysts during reduction by ammonia and oxidation by nitric oxide or oxygen at elevated temperatures was studied. The heat evolved during adsorption, reduction, and oxidation was measured by means of a differential scanning calorimeter. Ammonia reduces the catalysts to a certain extent under the formation of Nâ and HâO. On the basis of the

  16. Site-selective surface reactions: nitric oxide reduction on Mo(110).

    PubMed

    Queeney, K; Friend, C M

    2000-11-01

    The catalytic reduction of NO(x) compounds formed in combustion processes is a critical factor in maintaining a clean environment. The introduction of the "catalytic converter" has been extremely effective in reducing these pollutants in automobile exhaust over the last two decades. Nevertheless, new environmental regulations have necessitated the development of processes that operate over a wider range of conditions and that are more efficient, so that NOx emissions can be reduced further. The need for new catalysts and processes has motivated a considerable number of studies of NO reduction using metal oxides as catalysts. In order to better understand the mechanisms for NO reduction on oxides, we have systematically studied the reactions of NO on thin-film oxides grown on Mo(110). By using a thin-film oxide, we are able to change the type of coordination sites that are available for NO binding and to use surface-sensitive spectroscopies to identify intermediates on the surface. We specifically explore the role of low-temperature NO coupling to a dinitrosyl species in our work and contrast this reaction to the higher temperature process, NO dissociation followed by nitrogen atom coupling. PMID:23696302

  17. 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.

  18. 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.

  19. Genome reduction in Leptospira borgpetersenii reflects limited transmission potential

    PubMed Central

    Bulach, Dieter M.; Zuerner, Richard L.; Wilson, Peter; Seemann, Torsten; McGrath, Annette; Cullen, Paul A.; Davis, John; Johnson, Matthew; Kuczek, Elizabeth; Alt, David P.; Peterson-Burch, Brooke; Coppel, Ross L.; Rood, Julian I.; Davies, John K.; Adler, Ben

    2006-01-01

    Leptospirosis is one of the most common zoonotic diseases in the world, resulting in high morbidity and mortality in humans and affecting global livestock production. Most infections are caused by either Leptospira borgpetersenii or Leptospira interrogans, bacteria that vary in their distribution in nature and rely on different modes of transmission. We report the complete genomic sequences of two strains of L. borgpetersenii serovar Hardjo that have distinct phenotypes and virulence. These two strains have nearly identical genetic content, with subtle frameshift and point mutations being a common form of genetic variation. Starkly limited regions of synteny are shared between the large chromosomes of L. borgpetersenii and L. interrogans, probably the result of frequent recombination events between insertion sequences. The L. borgpetersenii genome is ?700 kb smaller and has a lower coding density than L. interrogans, indicating it is decaying through a process of insertion sequence-mediated genome reduction. Loss of gene function is not random but is centered on impairment of environmental sensing and metabolite transport and utilization. These features distinguish L. borgpetersenii from L. interrogans, a species with minimal genetic decay and that survives extended passage in aquatic environments encountering a mammalian host. We conclude that L. borgpetersenii is evolving toward dependence on a strict host-to-host transmission cycle. PMID:16973745

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

    PubMed

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

    2013-03-01

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

  1. Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.; Mann, C.J.

    2000-03-01

    Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial Fe(III) content remained in the columns at the end of the experiment. The near-quantitative removal of Fe was visibly evidenced by extensive bleaching of color from the sand in the columns. In contrast to the column reactors, Fe(II) production quickly reached an asymptote in batch cultures, and only (13.0 {+-} 2.2)% (n = 3) of the Fe(III) oxide content was reduced. Sustained bacterial-cell growth occurred in the column reactors, leading to the production and export of a quantity of cells 100-fold greater than that added during inoculation. Indirect estimates of cell growth, based on the quantity of Fe(III) reduced, suggest that only an approximate doubling of initial cell abundance was likely to have occurred in the batch cultures. Their results indicate that removal of biogenic Fe(II) via aqueous-phase transport in the column reactors decreased the passivating influence of surface-bound Fe(II) on oxide reduction activity, thereby allowing a dramatic increase in the extent of Fe(III) oxide reduction and associated bacterial growth. These findings have important implications for understanding the fate of organic and inorganic contaminants whose geochemical behavior is linked to Fe(III) oxide reduction.

  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. 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.

  4. Reduction of a polar oxide surface in a strong DC-field

    NASA Astrophysics Data System (ADS)

    Steurer, Wolfram; Surnev, Svetlozar; Barcaro, Giovanni; Fortunelli, Alessandro; Netzer, Falko P.

    2011-03-01

    Polar oxide surfaces are of fundamental scientific interest because of their inherent instability in bulk samples on electrostatic grounds. Here we report first experimental evidence of field-induced reduction of a polar oxide surface by applying homogeneous external DC-fields. Ultrathin Ni-oxide nanostructures immersed into an Ag(100) substrate have been grown by reactive evaporation and have subsequently been exposed to electric fields in the range of 0.5-1.6 V/nm. We achieve such high fields in a setup resembling a plate capacitor where the Ag(100) substrate (with the deposited NiO film) acts as the cathode with a counter electrode placed 800nm apart. For fields exceeding the threshold of 0.9 V/nm, oxygen atoms are torn away from the surface, thus, efficiently reducing the initially highly-ordered Ni-oxide film. The remaining Ni atoms on the surface are highly mobile and cluster together. No oxide reduction occurs if the field polarity is inverted. This work is supported by the ERC Advanced Grant ``SEPON.''

  5. 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.

  6. Hydrogen peroxide-induced reduction of delayed rectifier potassium current in hippocampal neurons involves oxidation of sulfhydryl groups.

    PubMed

    Hasan, Sonia M K; Redzic, Zoran B; Alshuaib, Waleed B

    2013-07-01

    This study examined the effect of H2O2 on the delayed rectifier potassium current (IKDR) in isolated hippocampal neurons. Whole-cell voltage-clamp experiments were performed on freshly dissociated hippocampal CA1 neurons of SD rats before and after treatment with H2O2. To reveal the mechanism behind H2O2-induced changes in IKDR, cells were treated with different oxidizing and reducing agents. External application of membrane permeable H2O2 reduced the amplitude and voltage-dependence of IKDR in a concentration dependent manner. Desferoxamine (DFO), an iron-chelator that prevents hydroxyl radical (OH) generation, prevented H2O2-induced reduction in IKDR. Application of the sulfhydryl-oxidizing agent 5,5 dithio-bis-nitrobenzoic acid (DTNB) mimicked the effect of H2O2. Sulfhydryl-reducing agents dithiothreitol (DTT) and glutathione (GSH) alone did not affect IKDR; however, DTT and GSH reversed and prevented the H2O2-induced inhibition of IKDR, respectively. Membrane impermeable agents GSH and DTNB showed effects only when added intracellularly identifying intracellular sulfhydryl groups as potential targets for hydroxyl-mediated oxidation. However, the inhibitory effects of DTNB and H2O2 at the positive test potentials were completely and partially abolished by DTT, respectively, suggesting an additional mechanism of action for H2O2, that is not shared by DTNB. In summary, this study provides evidence for the redox modulation of IKDR, identifies hydroxyl radical as an intermediate oxidant responsible for the H2O2-induced decrease in current amplitude and identifies intracellular sulfhydryl groups as an oxidative target. PMID:23688542

  7. A kinetic model for bacterial Fe(III) oxide reduction in batch cultures

    NASA Astrophysics Data System (ADS)

    Hacherl, Eric L.; Kosson, David S.; Cowan, Robert M.

    2003-04-01

    A model has been developed describing the microbial reduction of solid-phase electron acceptors (Fe(III) oxides) as well as dissolved electron acceptors (chelated Fe(III) or organic electron shuttles) in Shewanella alga BrY. The model utilized a multiple-substrate, Monod kinetics formulation. The Monod description of solid Fe(III) reduction requires a normalization of surface Fe concentration to biomass concentration in order to describe the "bioavailable" Fe(III) concentration. The model also contains provisions for irreversible sorption of Fe(II) to Fe(III) oxide surfaces and for the precipitation of Fe(III) carbonates. The loss of bioavailable Fe(III) due to sorption of Fe(II) was found to be minor, even for highly sorptive amorphous Fe(III) oxyhydroxides. However, the final extent of microbial reduction is very sensitive to the rate of siderite precipitation, assuming that siderite precipitation could partially occlude Fe(III) surface sites. The use of a multisubstrate Monod kinetics model enabled an evaluation of the effects of electron shuttles on solid Fe(III) reduction. Because the electron shuttle is recycled, very small additions can greatly increase the overall rate of solid Fe(III) reduction.

  8. 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.

  9. Personal carbon trading: a potential "stealth intervention" for obesity reduction?

    PubMed

    Egger, Garry

    2007-08-01

    The obesity epidemic and global warming are linked through energy use. A personal carbon trading scheme aimed at reducing fossil fuel usage could act as a "stealth intervention" for reducing obesity by increasing personal energy use. Such a scheme would complement a corporate "cap and trade" system for carbon emissions, which should increase the relative price of processed, energy-dense foods. The scheme would work by reducing global carbon emissions to a sustainable level (contraction), while offering potential for trade of emission rights between frugal and profligate users of non-renewable energy (convergence). A key goal would be changed attitudes to conspicuous (and obesogenic) consumption. Adoption of the scheme would make healthy choices the easy choice. PMID:17680749

  10. ADVANCED OXIDATION OF REFRACTORY ORGANICS IN LEACHATE – POTENTIAL METHODS AND EVALUATION OF BIODEGRADABILITY OF THE REMAINING SUBSTRATE

    Microsoft Academic Search

    M. Hagman; E. Heander; J. la C. Jansen

    2008-01-01

    An assessment of potential methods suitable for degradation and\\/or reduction of refractory organics was performed on landfill leachate from SYSAV AB, Malmö, Sweden. Pretreatment of the leachate was performed in a sequence batch reactor designed for nitrification in activated sludge. Oxidation of the leachate was then O3, O3\\/pH adjustment (pH 9 and 10), H2O2, O3\\/H2O2 and performic acid in lab?scale

  11. Oxidative dissolution potential of biogenic and abiogenic TcO{sub 2} in subsurface sediments.

    SciTech Connect

    Fredrickson, J. K.; Zachara, J. M.; Plymale, A. E.; Heald, S. M.; McKinley, J. P.; Kennedy, D. W.; Liu, C.; Nachimuthu, P. (X-Ray Science Division); ( PSC-USR); (PNNL)

    2009-04-01

    Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O{sub 4}{sup -}] and less mobile in the reduced form [Tc(IV)O{sub 2} {center_dot} nH{sub 2}O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO{sub 2}-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 {micro}m-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O{sub 2} into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.

  12. 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.

  13. HDR reservoir flow impedance and potentials for impedance reduction

    SciTech Connect

    DuTeau, R.; Brown, D.

    1993-06-01

    The data from flow tests which employed two different production zones in a well at Fenton Hill indicates the flow impedance of a wellbore zone damaged by rapid depressurization was altered, possibly by pressure spallation, which appears to have mechanically propped the joint apertures of outlet flow paths intersecting the altered wellbore. The rapid depressurization and subsequent flow test data derived from the damaged well has led to the hypothesis that pressure spallation and the resultant mechanical propping of outlet flow paths reduced the outlet flow impedance of the damaged wellbore. Furthermore, transient pressure data shows the largest pressure drop between the injection and production wellheads occurs near the production wellbore, so lowering the outlet impedance by increasing the apertures of outlet flow paths will have the greatest effect on reducing the overall reservoir impedance. Fenton Hill data also reveals that increasing the overall reservoir pressure dilates the apertures of flow paths, which likewise serves to reduce the reservoir impedance. Data suggests that either pressure dilating the wellbore connected joints with high production wellhead pressure, or mechanically propping open the outlet flow paths will increase the near-wellbore permeability. Finally, a new method for calculating and comparing near-wellbore outlet impedances has been developed. Further modeling, experimentation, and engineered reservoir modifications, such as pressure dilation and mechanical propping, hold considerable potential for significantly improving the productivity of HDR reservoirs.

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

    Microsoft Academic Search

    Sasha Stankovich; Dmitriy A. Dikin; Richard D. Piner; Kevin A. Kohlhaas; Alfred Kleinhammes; Yuanyuan Jia; Yue Wu; SonBinh T. Nguyen; Rodney S. Ruoff

    2007-01-01

    Reduction of a colloidal suspension of exfoliated graphene oxide sheets in water with hydrazine hydrate results in their aggregation and subsequent formation of a high-surface-area carbon material which consists of thin graphene-based sheets. The reduced material was characterized by elemental analysis, thermo-gravimetric analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, NMR spectroscopy, Raman spectroscopy, and by electrical conductivity measurements.

  15. Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors

    Microsoft Academic Search

    ERIC E. RODEN; MATILDE M. URRUTIA; CARROLL J. MANN

    2000-01-01

    Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial

  16. The efficacy of Trypsin: Chymotrypsin preparation in the reduction of oxidative damage during burn injury

    Microsoft Academic Search

    B. Latha; Mathangi Ramakrishnan; V. Jayaraman; Mary Babu

    1998-01-01

    This study was mainly aimed to investigate the efficacy of trypsin:chymotrypsin to elicit anti-oxidant properties. In our earlier studies it was observed that the enzyme preparation exhibited an anti-inflammatory action as there was a remarkable reduction in oedema formation and tissue destruction. This led to further study on the amount of lipid peroxidation products formed and the levels of enzymatic

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

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtlu

    2001-09-01

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments indicated that manganese is a more effective promoter than rhodium on the supported copper oxide-ceria catalysts under study; the effectiveness of the promoter increases with the increase in Ce/Cu ratio. The TPD profiles of the unpromoted catalyst (Cu/Ce=3) is different than those promoted with 0.1% rhodium.

  18. Low-temperature aluminum reduction of graphene oxide, electrical properties, surface wettability, and energy storage applications.

    PubMed

    Wan, Dongyun; Yang, Chongyin; Lin, Tianquan; Tang, Yufeng; Zhou, Mi; Zhong, Yajuan; Huang, Fuqiang; Lin, Jianhua

    2012-10-23

    Low-temperature aluminum (Al) reduction is first introduced to reduce graphene oxide (GO) at 100-200 °C in a two-zone furnace. The melted Al metal exhibits an excellent deoxygen ability to produce well-crystallized reduced graphene oxide (RGO) papers with a low O/C ratio of 0.058 (Al-RGO), compared with 0.201 in the thermally reduced one (T-RGO). The Al-RGO papers possess outstanding mechanical flexibility and extremely high electrical conductivities (sheet resistance R(s) ~ 1.75 ?/sq), compared with 20.12 ?/sq of T-RGO. More interestingly, very nice hydrophobic nature (90.5°) was observed, significantly superior to the reported chemically or thermally reduced papers. These enhanced properties are attributed to the low oxygen content in the RGO papers. During the aluminum reduction, highly active H atoms from H(2)O reacted with melted Al promise an efficient oxygen removal. This method was also applicable to reduce graphene oxide foams, which were used in the GO/SA (stearic acid) composite as a highly thermally conductive reservoir to hold the phase change material for thermal energy storage. The Al-reduced RGO/SnS(2) composites were further used in an anode material of lithium ion batteries possessing a higher specific capacity. Overall, low-temperature Al reduction is an effective method to prepare highly conductive RGO papers and related composites for flexible energy conversion and storage device applications. PMID:22984901

  19. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

    PubMed

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-08-15

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 ?M for methane and 8.7 ± 1.5 ?M for nitrite. PMID:26048927

  20. 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

  1. Nitrate reduction to nitrite, nitric oxide and ammonia by gut bacteria under physiological conditions.

    PubMed

    Tiso, Mauro; Schechter, Alan N

    2015-01-01

    The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome links diet and health. PMID:25803049

  2. 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

  3. 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.

  4. Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts

    Microsoft Academic Search

    N. Apostolescu; B. Geiger; K. Hizbullah; M. T. Jan; S. Kureti; D. Reichert; F. Schott; W. Weisweiler

    2006-01-01

    In this study, new Fe2O3 based materials are developed for the selective catalytic reduction (SCR) of NOx by NH3 in diesel exhaust. As a result of the catalyst screening, performed in a synthetic model exhaust, ZrO2 is considered to be the most effective carrier for Fe2O3. The modification of the Fe2O3\\/ZrO2 system with tungsten leads to drastic increase of SCR

  5. Compositional engineering of perovskite oxides for highly efficient oxygen reduction reactions.

    PubMed

    Chen, Dengjie; Chen, Chi; Zhang, Zhenbao; Baiyee, Zarah Medina; Ciucci, Francesco; Shao, Zongping

    2015-04-29

    Mixed conducting perovskite oxides are promising catalysts for high-temperature oxygen reduction reaction. Pristine SrCoO3-? is a widely used parent oxide for the development of highly active mixed conductors. Doping a small amount of redox-inactive cation into the B site (Co site) of SrCoO3-? has been applied as an effective way to improve physicochemical properties and electrochemical performance. Most findings however are obtained only from experimental observations, and no universal guidelines have been proposed. In this article, combined experimental and theoretical studies are conducted to obtain fundamental understanding of the effect of B-site doping concentration with redox-inactive cation (Sc) on the properties and performance of the perovskite oxides. The phase structure, electronic conductivity, defect chemistry, oxygen reduction kinetics, oxygen ion transport, and electrochemical reactivity are experimentally characterized. In-depth analysis of doping level effect is also undertaken by first-principles calculations. Among the compositions, SrCo0.95Sc0.05O3-? shows the best oxygen kinetics and corresponds to the minimum fraction of Sc for stabilization of the oxygen-vacancy-disordered structure. The results strongly support that B-site doping of SrCoO3-? with a small amount of redox-inactive cation is an effective strategy toward the development of highly active mixed conducting perovskites for efficient solid oxide fuel cells and oxygen transport membranes. PMID:25849591

  6. Probing the oxidation reduction properties of terrestrially and microbially derived dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Fimmen, Ryan L.; Cory, Rose M.; Chin, Yu-Ping; Trouts, Tamara D.; McKnight, Diane M.

    2007-06-01

    Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by 13C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of p Ka values.

  7. 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.

  8. Low potential Li insertion in transition metal oxides

    SciTech Connect

    Leroux, F.; Nazar, L.F.

    1998-07-01

    Low-potential Li insertion materials comprised of molybdenum oxides (A{sub x}MoO{sub 3}) have been prepared by a chimie douce route. Li insertion below 200 mV is associated with dramatic transformation of the structure, leading to a material which displays good cycloability with a high reversible specific capacity of 940 mA/g in the voltage window 3.0--0.005V (volumetric capacity of 4,000 mAh/cc), albeit with notable polarization on charge. The structural and compositional changes on discharge to 200 mV have been studied by a combination of XRD, and XAS. The interlayer ions have also been exchanged for Sn, and the electrochemical characteristics of these materials are compared with the alkali derivatives.

  9. Potentially toxic element release by fenton oxidation of sewage sludge.

    PubMed

    Andrews, J P; Asaadi, M; Clarke, B; Ouki, S

    2006-01-01

    The presence, in sewage sludge, of excess levels of the potentially toxic elements (PTE) copper, zinc, chromium, cadmium, nickel, lead and mercury, could impact on our ability to recycle these residues in the future. Far stricter limits on the levels of PTEs are likely in proposed legislation. A method involving the dosing of Fenton's reagent, a mixture of ferrous iron and hydrogen peroxide, under acidic conditions was evaluated for its potential to reduce metal levels. The [Fe]:[H2O2] (w/w) ratio was found to give a good indication of the percentage copper and zinc elution obtainable. Sites with no iron dosing as part of wastewater treatment required extra iron to be added in order to initiate the Fenton's reaction. A significant reduction, in excess of 70%, of the copper and zinc was eluted from both raw primary and activated sludge solid fractions. Cadmium and nickel could be reduced to below detection limits but elution of mercury, lead and chromium was less than 40%. The iron catalyst concentration was found to be a crucial parameter. This process has the potential to reduce the heavy metal content of the sludge and allow the recycling of sludge to continue in a sustainable manner. PMID:17087386

  10. Theoretical study of the reduction of nitric oxide in an A-type flavoprotein.

    PubMed

    Blomberg, L Mattias; Blomberg, Margareta R A; Siegbahn, Per E M

    2007-01-01

    The mechanism for the reduction of nitric oxide to nitrous oxide and water in an A-type flavoprotein (FprA) in Moorella thermoacetica, which has been proposed to be a scavenging type of nitric oxide reductase, has been investigated using density functional theory (B3LYP). A dinitrosyl complex, [{FeNO}(7)](2), has previously been proposed to be a key intermediate in the NO reduction catalyzed by FprA. The electrons and protons involved in the reduction were suggested to "super-reduce" the dinitrosyl intermediate to [{FeNO}(8)](2) or the corresponding diprotonated form, [{FeNO(H)}(8)](2). In this type of mechanism the electron and/or proton transfers will be a part of the rate-determining step. In the present study, on the other hand, a reaction mechanism is suggested in which N(2)O can be formed before the protons and electrons enter the catalytic cycle. One of the irons in the diiron center is used to stabilize the formation of a hyponitrite dianion, instead of binding a second NO. Cleaving the N-O bond in the hyponitrite dianion intermediate is the rate-determining step in the proposed reaction mechanism. The barrier of 16.5 kcal mol(-1) is in good agreement with the barrier height of the experimental rate-determining step of 14.8 kcal mol(-1). The energetics of some intermediates in the "super-reduction" mechanism and the mechanism proceeding via a hyponitrite dianion are compared, favoring the latter. It is also discussed how to experimentally discriminate between the two mechanisms. PMID:16957917

  11. The efficacy of trypsin: chymotrypsin preparation in the reduction of oxidative damage during burn injury.

    PubMed

    Latha, B; Ramakrishnan, M; Jayaraman, V; Babu, M

    1998-09-01

    This study was mainly aimed to investigate the efficacy of trypsin:chymotrypsin to elicit anti-oxidant properties. In our earlier studies it was observed that the enzyme preparation exhibited an anti-inflammatory action as there was a remarkable reduction in oedema formation and tissue destruction. This led to further study on the amount of lipid peroxidation products formed and the levels of enzymatic and non-enzymatic anti-oxidants and relative trace element contents of copper, selenium, iron and zinc during administration of the enzyme preparation. Decreased formation of lipid peroxidation products was observed in treated group in comparison with the untreated group. Higher levels of enzymatic anti-oxidants mainly super oxide dismutase, catalase, glutathione peroxidase and glutathione-s-transferase and non-enzymatic antioxidant namely ceruloplasmin persisted for a longer period of time in the treated group than in the untreated group. No statistical significance was observed in non-enzymatic antioxidants viz. ascorbic acid and tocopherol levels in both the groups. Increased serum copper and selenium levels in the treated group could be related to higher levels of the ceruloplasmin and glutathione peroxidase observed in the treated group. The above studies support the finding that treatment with the enzyme preparation reduced tissue destruction leading to decreased formation of free radicals and subsequent effective scavenging of free radicals by the higher levels of enzymatic and non-enzymatic anti-oxidants. PMID:9776092

  12. 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...

  13. Porphyrin-based graphene oxide frameworks with ultra-large d-spacings for the electrocatalyzation of oxygen reduction reaction.

    PubMed

    Yao, Bowen; Li, Chun; Ma, Jun; Shi, Gaoquan

    2015-07-15

    Graphene oxide frameworks (GOFs) have attracted a great deal of attention because of their unique functional building blocks, and tunable structures and properties. Herein, a series of porphyrin-based GOFs with crystalline lamellar structures were synthesized via esterification between boronic acid groups of porphyrins and hydroxyl groups of GO sheets. These GOFs have ultra-large d-spacings of up to 26.0 Å, and they were reduced by facile electrochemical reduction. The resulting reduced GOFs (rGOFs) can be used as catalysts for oxygen reduction reaction (ORR). Electrochemical reduction improved the conductivities of GOFs, accelerating the charge transfer of ORR. The rGOF with Co-porphyrin showed the most positive onset potential of ORR at 0.89 V (vs. RHE, reversible hydrogen electrode), while the rGOF with Fe-porphyrin exhibited the highest catalytic efficiency through an approximately four-electron process. This study provides a new insight for the development of GOFs using multi-functional macrocyclic molecules, revealing their promising applications in electrocatalysts. PMID:26145727

  14. 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.

  15. 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

  16. Pulsed laser irradiation for environment friendly reduction of graphene oxide suspensions

    NASA Astrophysics Data System (ADS)

    Ghadim, Ehsan Ezzatpour; Rashidi, Nasim; Kimiagar, Salimeh; Akhavan, Omid; Manouchehri, Firouzeh; Ghaderi, Elham

    2014-05-01

    Graphene oxide (GO) sheets were synthesized through a modified Hummers' method. Using high resolution transmission electron microscopy the thickness of the GO sheets in a multilayer structure of stacked GO sheets was found ˜0.8 nm. A nanosecond pulsed laser (with wavelength of 532 nm and average power of 0.3 W) was applied for effective and environment friendly reduction of the GO sheets in an ammonia solution (pH ˜9) at room temperature conditions. The deoxygenation of the GO sheets by the pulsed laser reduction method was confirmed by using UV-visible, Fourier transform infrared, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis. Based on XPS analysis, the O/C ratio of the GO sheets decreased from 49% to 21% after 10 min laser irradiation. This reduction efficiency was comparable with the efficiency achieved by hydrazine which yielded the O/C ratio of 15% at 80 °C after 10 min. Using Raman spectroscopy it was found that the pulsed laser reduction method resulted in nearly no aggregation of the reduced GO sheets in the ammonia solution. These results can help to further promotion and application of pulsed lasers in environment friendly reduction of GO.

  17. Quinone reduction by Rhodothermus marinus succinate:menaquinone oxidoreductase is not stimulated by the membrane potential

    SciTech Connect

    Fernandes, Andreia S. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); Konstantinov, Alexander A. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); A.N. Belozersky Institute of Physico-Chemical Biology, Moscow State University, 119992 Moscow (Russian Federation); Teixeira, Miguel [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal); Pereira, Manuela M. [Instituto de Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Av. da Republica, Apartado 127, 2784-505 Oeiras (Portugal)]. 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.

  18. 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.

  19. Advanced oxidation of refractory organics in leachate--potential methods and evaluation of biodegradability of the remaining substrate.

    PubMed

    Hagman, M; Heander, E; Jansen, J La C

    2008-09-01

    An assessment of potential methods suitable for degradation and/or reduction of refractory organics was performed on landfill leachate from SYSAV AB, Malmö, Sweden. Pretreatment of the leachate was performed in a sequence batch reactor designed for nitrification in activated sludge. Oxidation of the leachate was then O3, O3/pH adjustment (pH 9 and 10), H2O2, O3/H2O2 and performic acid in lab-scale reactors. The degradation of organic material was followed with chemical oxygen demand (COD) measurements for all experiments except for the performic acid treatment for which total organic carbon (TOC) measurements were used. The potential degradation of refractory organics into biodegradable organic material was analysed by subsequent oxygen uptake rate (OUR) measurements in laboratory batch reactors. Ozonation of biologically pre-treated leachate increased reduction of the organic material. The most biodegradable organic material was produced after oxidation with only ozone and ozonation at pH 9. Performic acid did not reduce the content of organic material in the leachate. However, a combination of biological pretreatment, chemical oxidation with O3/H2O2 and a subsequent biological process resulted in the most efficient oxidation method for the tested leachate. PMID:18844121

  20. An inorganic geochemical argument for coupled anaerobic oxidation of methane and iron reduction in marine sediments.

    PubMed

    Riedinger, N; Formolo, M J; Lyons, T W; Henkel, S; Beck, A; Kasten, S

    2014-03-01

    Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere. PMID:24460948

  1. Room temperature reduction of graphene oxide by formic acid catalyzed by platinum nanoparticles.

    PubMed

    Wang, Yinjie; Liul, Jincheng; Liu, Lei; Zhang, Tong; Sun, Darren D

    2013-04-01

    Graphene oxide (GO) was reduced by stirring the solution contaning GO sheets with platinum (Pt) nanoparticles and formic acid at room temperature for 72 h. The resulting reduced graphene oxide-Pt (RGO-Pt) nanocomposites were characterized, and it was found that the Pt nanoparticles of size 4-6 nm were anchored onto the RGO sheets. The reduction of GO was facilitated by formic acid catalysed by the Pt nanoparticles. The reduction level of the GO sheets was related to the pH of the mixed solution, and higher pH would induce higher reduction level of the GO sheets. The RGO-Pt nanocomposites synthesized at pH 4 and pH 7 exhibit large electrochemically active surface area of 49.45 m2/g and 56.78 m2/g, and high I(f)/I(b) ratio of 2.36 and 2.87 indicating high electrocatalytic activities. This paper presents a new energy efficient way to reduce GO and produce RGO-Pt for fuel cell and other applications. PMID:23763187

  2. 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.

  3. Oxide shell reduction and magnetic property changes in core-shell Fe nanoclusters under ion irradiation

    SciTech Connect

    Sundararajan, Jennifer A.; Kaur, Maninder; Qiang, You, E-mail: youqiang@uidaho.edu [Department of Physics, University of Idaho, Moscow, Idaho 83844 (United States); Jiang, Weilin [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 (United States); McCloy, John S. [School of Mechanical and Materials Engineering, Washington State University, Pullman, Washington 99164 (United States)

    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.

  4. 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

  5. Nitric oxide as a potential biomarker in inflammatory bowel disease

    PubMed Central

    Avdagi?, Nesina; Za?iragi?, Asija; Babi?, Nermina; Huki?, Mirsada; Šeremet, Mensura; Lepara, Orhan; Nakaš-I?indi?, Emina

    2013-01-01

    The aim of this study was to investigate changes in serum nitric oxide (NO) concentration in inflammatory bowel diseases (IBD) patients and its use as potential biomarker in differential diagnosis of ulcerative colitis (UC) and Crohn’s disease (CD) and in disease activity assessment. In 60 patients of both genders – 30 with ulcerative colitis and 30 with Crohn’s disease - and 30 controls serum nitric oxide concentration was determined by measuring nitrite concentration, a stable metabolic product of NO with oxygen. Conversion of nitrates (NO3-) to nitrites (NO2-) was done with elementary zinc. The nitrite concentration was determined by classic colorimetrical Griess reaction. Median serum NO concentration was statistically different (p=0,0005) between UC patients (15.25 ?mol/L; 13.47 – 19.88 ?mol/L), CD patients (14.54 ?mol/L; 13.03 –16.32 ?mol/L) and healthy controls (13.29 ?mol/L; 12.40 – 13.92 ?mol/L). When active UC and CD patients were compared with inactive UC and CD patients respectively a significant difference in serum NO level was found (p=0.0005). With a cut-off level of 17.39 ?mol/L NO had a sensitivity of 100% and a specificity of 100% in discriminating between active and inactive UC patients. With cut-off value of 14.01 ?mol/L serum NO level had a sensitivity of 88% and a specificity of 69% in distinguishing between patients with active CD and inactive CD. Serum NO concentration is a minimally invasive and rapid tool for discriminating between active and inactive IBD patients and could be used as useful biomarker in monitoring of disease activity in IBD patients. PMID:23448603

  6. Insight into the Interaction of Graphene Oxide with Serum Proteins and the Impact of the Degree of Reduction and Concentration.

    PubMed

    Wei, Xue-Qin; Hao, Li-Ying; Shao, Xiao-Ru; Zhang, Quan; Jia, Xiao-Qin; Zhang, Zhi-Rong; Lin, Yun-Feng; Peng, Qiang

    2015-06-24

    As novel applied nanomaterials, both graphene oxide (GO) and its reduced form (rGO) have attracted global attention, because of their excellent properties. However, the lack of comprehensive understanding of their interactions with biomacromolecules highly limits their biomedical applications. This work aims to initiate a systematic study on the property changes of GO/rGO upon interaction with serum proteins and on how their degree of reduction and exposure concentration affect this interaction, as well as to analyze the possible biomedical impacts of the interaction. We found that the adsorption of proteins on GO/rGO occurred spontaneously and rapidly, leading to significant changes in size, zeta potential, and morphology. Compared to rGO, GO showed a higher ability in quenching intrinsic fluorescence of serum proteins in a concentration-dependent manner. The protein adsorption efficiency and the types of associated proteins varied, depending on the degree of reduction and concentration of graphene. Our findings indicate the importance of evaluating the potential protein adsorption before making use of GO/rGO in drug delivery, because the changed physicochemical properties after protein adsorption will have significant impacts on safety and effectiveness of these delivery systems. On the other hand, this interaction can also be used for the separation, purification, or delivery of certain proteins. PMID:26029973

  7. 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.

  8. Efficient photocatalytic selective nitro-reduction and C-H bond oxidation over ultrathin sheet mediated CdS flowers.

    PubMed

    Pahari, Sandip Kumar; Pal, Provas; Srivastava, Divesh N; Ghosh, Subhash Ch; Panda, Asit Baran

    2015-06-11

    We report here a visible light driven selective nitro-reduction and oxidation of saturated sp(3) C-H bonds using ultrathin (0.8 nm) sheet mediated uniform CdS flowers as catalyst under a household 40 W CFL lamp and molecular oxygen as oxidant. The CdS flowers were synthesized using a simple surfactant assisted hydrothermal method. PMID:26024214

  9. [Fundamental studies in oxidation-reduction in relation to water photolysis]. Progress report, June 26, 1989--November 1, 1990

    SciTech Connect

    Hurst, J.K.

    1990-12-31

    Objective is to solve problems in photoredox catalysis pertinent to developing membrane-base photoconversion/photostorage systems. The research is divided into: Physical studies (light scattering) on viologen-doped vesicles, transmembrane oxidation-reduction mechanisms, interfacial charge recombination, water oxidation catalysts.

  10. Iodide Oxidation and Iodine Reduction Mediated by Horseradish Peroxidase in the Presence of Ethylenediaminetetraacetic Acid (EDTA): the Superoxide Effect

    Microsoft Academic Search

    H. C. Chang; J. A. Bumpus

    Ethylenediaminetetraacetic acid (EDTA) is an inhibitor of iodide (I-) oxidation that is catalyzed by horseradish peroxidase (HRP). HRP-mediated iodine (I2) reduction and triiodide (I3 - ) disappearance occur in the presence of this inhibitor. It is interesting that in the presence of EDTA, HRP produces superoxide radical, a reactive oxygen species that is required for iodine reduction. Substitution of potassium

  11. HYDROGEN-BASED, HOLLOW-FIBER MEMBRANE BIOFILM REACTOR FOR REDUCTION OF PERCHLORATE AND OTHER OXIDIZED CONTAMINANTS

    E-print Network

    Nerenberg, Robert

    HYDROGEN-BASED, HOLLOW-FIBER MEMBRANE BIOFILM REACTOR FOR REDUCTION OF PERCHLORATE AND OTHER tested a hydrogen-based, hollow-fiber membrane biofilm reactor (MBfR) for reduction of perchlorate these and other oxidized contaminants in drinking water. Key Words: Biofilm reactor, hollow-fiber membrane

  12. Monoclinic hafnium oxynitride supported on reduced graphene oxide to catalyse the oxygen reduction reaction in acidic media.

    PubMed

    Chisaka, M; Sasaki, H; Muramoto, H

    2014-10-14

    Monoclinic HfO2 nanoparticles were doped with nitrogen via hydrothermal treatment that avoided high-cost pyrolysis with NH3 gas in order to develop a novel oxygen reduction reaction catalyst for use in acidic media. Catalyst size reduction was achieved using a reduced graphene oxide support, and activity above 0.8 V was obtained. PMID:25167377

  13. Metal oxide-based nanoparticles: revealing their potential to enhance oil recovery in different wettability systems

    NASA Astrophysics Data System (ADS)

    Hendraningrat, Luky; Torsæter, Ole

    2015-02-01

    This paper presents systematic studies of hydrophilic metal oxide nanoparticles (NPs) dispersed in brine intended to reveal their potential to enhance oil recovery (EOR) in various rock wettability systems. The stability in suspension (nanofluid) of the NPs has been identified as a key factor related to their use as an EOR agent. Experimental techniques have been developed for nanofluid stability using three coupled methods: direct visual observation, surface conductivity and particle size measurements. The use of a dispersant has been investigated and has been shown to successfully improve metal oxide nanofluid stability as a function of its concentration. The dispersant alters the nanofluid properties, i.e. surface conductivity, pH and particle size distribution. A two-phase coreflood experiment was conducted by injecting the stable nanofluids as a tertiary process (nano-EOR) through core plugs with various wettabilities ranging from water-wet to oil-wet. The combination of metal oxide nanofluid and dispersant improved the oil recovery to a greater extent than either silica-based nanofluid or dispersant alone in all wettability systems. The contact angle, interfacial tension (IFT) and effluent were also measured. It was observed that metal oxide-based nanofluids altered the quartz plates to become more water-wet, and the results are consistent with those of the coreflood experiment. The particle adsorption during the transport process was identified from effluent analysis. The presence of NPs and dispersant reduced the IFT, but its reduction is sufficient to yield significant additional oil recovery. Hence, wettability alteration plays a dominant role in the oil displacement mechanism using nano-EOR.

  14. 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.

  15. 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

  16. 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 ...

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

    E-print Network

    Standridge, Brad Lee

    1994-01-01

    II ("B") test of 300 ppm Hz. . 59 Fig. 20. Concentration of NO, NzO, NOz, CO, and total nitrogen oxides (NO+NzO+NOz) as a function of average reactor temperature for the Phase II ("B") test of 900 pptn Hz, , 60 Fig. 21 Percent NO, reduction as a.../in x 100). . . . . . 121 Fig. 60. Concentration of HNCO, CO, and COz as a function of average reactor temperature for the test of 665 ppm CzH&OH The ratio of the summation of outlet HNCO, CO, and COz concentrations to the nominal inlet sum of all...

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

    SciTech Connect

    Liu Jian; Zhou Jinming; Ye Changqing [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Organic Solids, Laboratory of New Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Li Mingzhu; Wang Jingxia; Jiang Lei; Song Yanlin [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Organic Solids, Laboratory of New Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

    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.

  19. 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.

  20. High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

    PubMed

    Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

    2015-03-01

    Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 ?mol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 ?mol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation. PMID:25256585

  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.

    2011-12-27

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

  2. 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.

  3. 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.

  4. On the worst case complexity of potential reduction algorithms for linear programming

    Microsoft Academic Search

    Dimitris Bertsimas; Xiaodong Luo

    1997-01-01

    There are several classes of interior point algorithms that solve linear programming problems in O(x\\/ffL) iterations. Among them, several potential reduction algorithms combine both theoretical (o(vr~L) iterations) and practical efficiency as they allow the flexibility of line searches in the potential function, and thus can lead to practical implementations. It is a significant open question whether interior point algorithms can

  5. Effect of bacterium Oceanospirillum on the corrosion potential and oxygen reduction of AISI 4340 steel

    E-print Network

    Popova, Snezana N.

    1992-01-01

    EFFECT OF BACTERIUM OCEANOSPIRILLUM ON THE CORROSION POTENTIAL AND OXYGEN REDUCI1ON OF AISI 4340 STEEL A Thesis by SNEZANA N. POPOVA Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment... of the requirements for the degree of MASTER OF SCIENCE December 1992 Major Subject: Chemical Engineering EFFECT OF BACTERIUM OCEANOSPIRILLUM ON THE CORROSION POTENTIAL AND OXYGEN REDUCTION OF AISI 4340 STEEL A Thesis by SNEZANA N. POPOVA Appmved as to style...

  6. 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.

  7. 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.

  8. 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...

  9. (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

  10. Integrated pedestrian countermeasures – Potential of head injury reduction combining passive and active countermeasures

    Microsoft Academic Search

    Rikard Fredriksson; Erik Rosén

    A rapid development of both pedestrian passive and active safety, such as pedestrian bonnets\\/airbags and autonomous braking, is in progress. The aim of this study was to investigate the potential pedestrian head injury reduction from hypothetical passive and active countermeasures compared to an integrated system. The German In-Depth Accident Study (GIDAS) database was queried from 1999 to 2008 for severely

  11. 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.

  12. Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent.

    PubMed

    Bachate, Sachin P; Nandre, Vinod S; Ghatpande, Niraj S; Kodam, Kisan M

    2013-02-01

    Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L(-1) Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L(-1) As(III) within 10 h in minimal medium. It also completely reduced 15 mg L(-1) Cr(VI) and oxidized 50 mg L(-1) of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species. PMID:23182111

  13. 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

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

    PubMed

    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

  15. 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.

  16. 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.

  17. 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

  18. Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules.

    SciTech Connect

    Genorio, B.; Strmcnik, D.; Subbaraman, R.; Tripkovic, D.; Karapetrov, G.; Stamenkovic, V. R.; Pejovnik, S.; Markovic, N. M.; Univ. Ljubljana; National Inst. of Chemistry

    2010-12-01

    The design of new catalysts for polymer electrolyte membrane fuel cells must be guided by two equally important fundamental principles: optimization of their catalytic behaviour as well as the long-term stability of the metal catalysts and supports in hostile electrochemical environments. The methods used to improve catalytic activity are diverse, ranging from the alloying and de-alloying of platinum to the synthesis of platinum core-shell catalysts. However, methods to improve the stability of the carbon supports and catalyst nanoparticles are limited, especially during shutdown (when hydrogen is purged from the anode by air) and startup (when air is purged from the anode by hydrogen) conditions when the cathode potential can be pushed up to 1.5 V. Under the latter conditions, stability of the cathode materials is strongly affected (carbon oxidation reaction) by the undesired oxygen reduction reaction (ORR) on the anode side. This emphasizes the importance of designing selective anode catalysts that can efficiently suppress the ORR while fully preserving the Pt-like activity for the hydrogen oxidation reaction. Here, we demonstrate that chemically modified platinum with a self-assembled monolayer of calix[4]arene molecules meets this challenging requirement.

  19. Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules

    NASA Astrophysics Data System (ADS)

    Genorio, Bostjan; Strmcnik, Dusan; Subbaraman, Ram; Tripkovic, Dusan; Karapetrov, Goran; Stamenkovic, Vojislav R.; Pejovnik, Stane; Markovi?, Nenad M.

    2010-12-01

    The design of new catalysts for polymer electrolyte membrane fuel cells must be guided by two equally important fundamental principles: optimization of their catalytic behaviour as well as the long-term stability of the metal catalysts and supports in hostile electrochemical environments. The methods used to improve catalytic activity are diverse, ranging from the alloying and de-alloying of platinum to the synthesis of platinum core-shell catalysts. However, methods to improve the stability of the carbon supports and catalyst nanoparticles are limited, especially during shutdown (when hydrogen is purged from the anode by air) and startup (when air is purged from the anode by hydrogen) conditions when the cathode potential can be pushed up to 1.5V (ref. 11). Under the latter conditions, stability of the cathode materials is strongly affected (carbon oxidation reaction) by the undesired oxygen reduction reaction (ORR) on the anode side. This emphasizes the importance of designing selective anode catalysts that can efficiently suppress the ORR while fully preserving the Pt-like activity for the hydrogen oxidation reaction. Here, we demonstrate that chemically modified platinum with a self-assembled monolayer of calix[4]arene molecules meets this challenging requirement.

  20. 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.

  1. Effect of set potential on hexavalent chromium reduction and electricity generation from biocathode microbial fuel cells.

    PubMed

    Huang, Liping; Chai, Xiaolei; Chen, Guohua; Logan, Bruce E

    2011-06-01

    Setting a biocathode potential at -300 mV improved the subsequent performance of an MFC for Cr(VI) reduction compared to a control (no set potential). With this set potential, the startup time was reduced to 19 days, the reduction of Cr(VI) was improved to 19.7 mg/L d, and the maximum power density was increased to 6.4 W/m(3) compared to the control (26 days, 14.0 mg/L d and 4.1 W/m(3)). Set potentials of -150 mV and -300 mV also improved system performance and led to similarly higher utilization of metabolic energy gained (PMEG) than set potentials of +200 mV and -450 mV. We observed putative pili at -150 and -300 mV potentials, and aggregated precipitates on bacterial surfaces in both poised and nonpoised controls. These tests show that there are optimal potentials that can be set for developing a Cr(VI) biocathode. PMID:21528902

  2. Reduction of Brain Mitochondrial ?-Oxidation Impairs Complex I and V in Chronic Alcohol Intake: The Underlying Mechanism for Neurodegeneration

    PubMed Central

    Haorah, James; Rump, Travis J.; Xiong, Huangui

    2013-01-01

    Neuropathy and neurocognitive deficits are common among chronic alcohol users, which are believed to be associated with mitochondrial dysfunction in the brain. The specific type of brain mitochondrial respiratory chain complexes (mRCC) that are adversely affected by alcohol abuse has not been studied. Thus, we examined the alterations of mRCC in freshly isolated mitochondria from mice brain that were pair-fed the ethanol (4% v/v) and control liquid diets for 7–8 weeks. We observed that alcohol intake severely reduced the levels of complex I and V. A reduction in complex I was associated with a decrease in carnitine palmitoyltransferase 1 (cPT1) and cPT2 levels. The mitochondrial outer (cPT1) and inner (cPT2) membrane transporter enzymes are specialized in acylation of fatty acid from outer to inner membrane of mitochondria for ATP production. Thus, our results showed that alterations of cPT1 and cPT2 paralleled a decrease ?-oxidation of palmitate and ATP production, suggesting that impairment of substrate entry step (complex I function) can cause a negative impact on ATP production (complex V function). Disruption of cPT1/cPT2 was accompanied by an increase in cytochrome C leakage, while reduction of complex I and V paralleled a decrease in depolarization of mitochondrial membrane potential (??, monitored by JC-1 fluorescence) and ATP production in alcohol intake. We noted that acetyl-L-carnitine (ALC, a cofactor of cPT1 and cPT2) prevented the adverse effects of alcohol while coenzyme Q10 (CoQ10) was not very effective against alcohol insults. These results suggest that understanding the molecular, biochemical, and signaling mechanisms of the CNS mitochondrial ?-oxidation such as ALC can mitigate alcohol related neurological disorders. PMID:23967116

  3. 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.

  4. Emission reduction from diesel engine using fumigation methanol and diesel oxidation catalyst.

    PubMed

    Zhang, Z H; Cheung, C S; Chan, T L; Yao, C D

    2009-07-15

    This study is aimed to investigate the combined application of fumigation methanol and a diesel oxidation catalyst for reducing emissions of an in-use diesel engine. Experiments were performed on a 4-cylinder naturally-aspirated direct-injection diesel engine operating at a constant speed of 1800 rev/min for five engine loads. The experimental results show that at low engine loads, the brake thermal efficiency decreases with increase in fumigation methanol; but at high loads, it slightly increases with increase in fumigation methanol. The fumigation method results in a significant increase in hydrocarbon (HC), carbon monoxide (CO), and nitrogen dioxide (NO(2)) emissions, but decrease in nitrogen oxides (NO(x)), smoke opacity and the particulate mass concentration. For the submicron particles, the total number of particles decreases. In all cases, there is little change in geometrical mean diameter of the particles. After catalytic conversion, the HC, CO, NO(2), particulate mass and particulate number concentrations were significantly reduced at medium to high engine loads; while the geometrical mean diameter of the particles becomes larger. Thus, the combined use of fumigation methanol and diesel oxidation catalyst leads to a reduction of HC, CO, NO(x), particulate mass and particulate number concentrations at medium to high engine loads. PMID:19446309

  5. Beam induced reduction of U(VI) during X-ray photoelectron spectroscopy: The utility of the U4f satellite structure for identifying uranium oxidation states in mixed valence uranium oxides

    Microsoft Academic Search

    Eugene S. Ilton; Jean-François Boily; Paul S. Bagus

    2007-01-01

    Reduction of UVI by the beam during X-ray photoelectron spectroscopy (XPS) is a commonly observed phenomenon. This can affect the determination of the U oxidation state, or states, in U oxides (or U compounds in general) and compromise the validity of peak parameters derived from UVI oxide standards. However, there is little quantitative information on the reduction kinetics and species

  6. High Glucose–Induced Oxidative Stress Increases Transient Receptor Potential Channel Expression in Human Monocytes

    PubMed Central

    Wuensch, Tilo; Thilo, Florian; Krueger, Katharina; Scholze, Alexandra; Ristow, Michael; Tepel, Martin

    2010-01-01

    OBJECTIVE Transient receptor potential (TRP) channel–induced cation influx activates human monocytes, which play an important role in the pathogenesis of atherosclerosis. In the present study, we investigated the effects of high glucose–induced oxidative stress on TRP channel expression in human monocytes. RESEARCH DESIGN AND METHODS Human monocytes were exposed to control conditions (5.6 mmol/l d-glucose), high glucose (30 mmol/l d-glucose or l-glucose), 100 ?mol/l peroxynitrite, or high glucose in the presence of the superoxide dismutase mimetic tempol (100 ?mol/l). TRP mRNA and TRP protein expression was measured using quantitative real-time RT-PCR and quantitative in-cell Western assay, respectively. Calcium influx and intracellular reactive oxygen species were measured using fluorescent dyes. RESULTS Administration of high d-glucose significantly increased reactive oxygen species. High d-glucose or peroxynitrite significantly increased the expression of TRP canonical type 1 (TRPC1), TRPC3, TRPC5, TRPC6, TRP melastatin type 6 (TRPM6), and TRPM7 mRNA and TRPC3 and TRPC6 proteins. High d-glucose plus tempol or high l-glucose did not affect TRP expression. Increased oxidative stress by lipopolysaccharide or tumor necrosis factor-? increased TRP mRNA expression, whereas the reduction of superoxide radicals using diphenylene iodonium significantly reduced TRP mRNA expression. Increased TRPC3 and TRPC6 protein expression was accompanied by increased 1-oleoyl-2-acetyl-sn-glycerol–induced calcium influx, which was blocked by the TRPC inhibitor 2-aminoethoxydiphenylborane. TRPC6 mRNA was significantly higher in monocytes from 18 patients with type 2 diabetes compared with 28 control subjects (P < 0.05). CONCLUSIONS High d-glucose–induced oxidative stress increases TRP expression and calcium influx in human monocytes, pointing to a novel pathway for increased activation of monocytes and hence atherosclerosis in patients with diabetes. PMID:20068131

  7. Mechanisms for Accessing Insoluble Fe(III) Oxide during Dissimilatory Fe(III) Reduction by Geothrix fermentans

    PubMed Central

    Nevin, Kelly P.; Lovley, Derek R.

    2002-01-01

    Mechanisms for Fe(III) oxide reduction were investigated in Geothrix fermentans, a dissimilatory Fe(III)-reducing microorganism found within the Fe(III) reduction zone of subsurface environments. Culture filtrates of G. fermentans stimulated the reduction of poorly crystalline Fe(III) oxide by washed cell suspensions, suggesting that G. fermentans released one or more extracellular compounds that promoted Fe(III) oxide reduction. In order to determine if G. fermentans released electron-shuttling compounds, poorly crystalline Fe(III) oxide was incorporated into microporous alginate beads, which prevented contact between G. fermentans and the Fe(III) oxide. G. fermentans reduced the Fe(III) within the beads, suggesting that one of the compounds that G. fermentans releases is an electron-shuttling compound that can transfer electrons from the cell to Fe(III) oxide that is not in contact with the organism. Analysis of culture filtrates by thin-layer chromatography suggested that the electron shuttle has characteristics similar to those of a water-soluble quinone. Analysis of filtrates by ion chromatography demonstrated that there was as much as 250 ?M dissolved Fe(III) in cultures of G. fermentans growing with Fe(III) oxide as the electron acceptor, suggesting that G. fermentans released one or more compounds capable of chelating and solubilizing Fe(III). Solubilizing Fe(III) is another strategy for alleviating the need for contact between cells and Fe(III) oxide for Fe(III) reduction. This is the first demonstration of a microorganism that, in defined medium without added electron shuttles or chelators, can reduce Fe(III) derived from Fe(III) oxide without directly contacting the Fe(III) oxide. These results are in marked contrast to those with Geobacter metallireducens, which does not produce electron shuttles or Fe(III) chelators. These results demonstrate that phylogenetically distinct Fe(III)-reducing microorganisms may use significantly different strategies for Fe(III) reduction. Thus, it is important to know which Fe(III)-reducing microorganisms predominate in a given environment in order to understand the mechanisms for Fe(III) reduction in the environment of interest. PMID:11976100

  8. Biogeochemistry of Fe and Tc Reduction and Oxidation in FRC Sediment

    SciTech Connect

    John M. Zachara; James K. Fredrickson; Ravi K. Kukkadapu; Steven C. Smith; David W. Kennedy

    2004-03-17

    The objectives are: (1) To rigorously characterize the distribution of Fe(II) and Fe(III) in FRC sediment. (2) To identify changes to Fe(II)/Fe(III) distribution and concentration resulting from DIRB activity. (3) To determine the dependence of Tc(VII) reduction rate on biogenic Fe(II) and it's forms. (4) To establish tendency of Tc(IV) and biogenic Fe(II) to oxidize and their effects on Tc immobilization. The mineralogic and chemical properties of the pristine, bioreduced, and chemically extracted FRC sediments were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray microscopy (XRM, at the PNC-CAT beamline at APS), Moessbauer spectroscopy, and scanning and transmission electron microscopy with lattice fringe imaging. Chemical extraction included dithionite-citrate-bicarbonate (DCB), acid ammonium oxalate (AAO), and hydroxylamine hydrochloride (HAH). The FRC sediment was incubated under anoxic conditions with the facultative dissimilatory metal-reducing bacterium Shewanella putrefaciens, strain CN32 in defined aqueous solutions/media with bicarbonate and PIPES buffers for time periods exceeding 75 d. Lactate was used as the electron donor. Aqueous and sorbed Fe(II) (ferrozine assay and 0.5 N HCl extraction) and Mn(II) (ICP-MS and 10 mM CuSO{sub 4} extraction), and pH were monitored to define the reduction progress and extent. The bioreduced materials were characterized using the abovementioned techniques. Bioreduced (pasteurized) sediment or chemically extracted/reduced sediment spiked with Fe(II) was washed with a PIPES buffer/electrolyte solution, and spiked with NaTc(VII)O{sub 4} to yield a concentration of 20 {micro}M. The Tc(VII)-spiked samples were agitated and equilibrated at 25 C and sampled over time to assess the Tc(VII) reduction rate. Selected sediment samples containing 20 {micro}M of reduced Tc [Tc(IV)] were subjected to oxidation by: (1) successive headspace replacements of air, and (2) open system equilibration with air. Removed aqueous samples were filtered (< 2 {micro}m) and counted to determine the Tc(VII) concentration. Thin sections of the bioreduced/chemically reduced Tc(VII) reacted/oxidized sediments were analyzed by backscattered electron microscopy and X-ray microspectroscopy.

  9. 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.

  10. Photocatalytic CO(2) reduction using non-titanium metal oxides and sulfides.

    PubMed

    Navalón, Sergio; Dhakshinamoorthy, Amarajothi; Alvaro, Mercedes; Garcia, Hermenegildo

    2013-04-01

    Titanium dioxide (TiO2 ) is by far the most widely used photocatalyst both for the degradation of pollutants and in the field of renewable energies for the production of solar fuels. However, TiO2 has strong limitations in CO2 reduction, particularly under visible light irradiation. The flat-band potential of electrons in the conduction band of TiO2 is lower than that required for CO2 reduction and, therefore, it seems appropriate to develop and validate materials other than TiO2 . In addition, the photoresponse of TiO2 requires photons of wavelengths in the UV range shorter than 380 nm and strategies to implement a visible-light photoresponse on TiO2 by doping have not been completely satisfactory particularly because of problems in reproducibility and stability of the materials. For these reasons, we focus in this Review on semiconductors other than TiO2 that show photocatalytic activity in CO2 reduction. Attention has been paid to the irradiation conditions to put the productivity data into context. The role of co-catalyst and heterojunctions to increase the efficiency of charge separation is also discussed. Our aim is to describe the state of the art in the field of photocatalytic CO2 reduction using materials other than TiO2 , trying to trigger further research in this area. PMID:23468280

  11. Action of the radiation from a pulsed lamp on air. Reduction in the breakdown potential

    Microsoft Academic Search

    G. A. Volkova; I. V. Podmoshenskii; T. Ya. Smolyar

    1978-01-01

    the vacuum-ultraviol et region and the propagation of thermal perturbations in the air were investigated. These phenomena can also bring about a reduction in the electric strength of air, which should certainly be observed, since even when air is illuminated by a spark, its breakdown potentials are reduced by 10-20% [3]. Since high-intensity pulsed lamps are widely employed and they

  12. Are thermodynamic cycles necessary for continuum solvent calculation of pKas and reduction potentials?

    PubMed

    Ho, Junming

    2015-01-28

    Continuum solvent calculations of pKas and reduction potentials usually entail the use of a thermodynamic cycle to express the reaction free energy in terms of gas phase energies and free energies of solvation. In this work, we present a systematic study comparing the solution phase free energy changes obtained in this manner with those directly computed within the SMD solvation model against a large test set of 117 pKas and 42 reduction potentials in water and DMSO. The inclusion of vibrational contributions in the free energy of solvation has a negligible impact on the accuracy of thermodynamic cycle predictions of pKas and reduction potentials. Additionally, when gas phase energies in the thermodynamic cycle are computed at more accurate levels of theory, very similar results (mean unsigned difference of 0.5 kcal mol(-1)) can be achieved when the high-level computations (MP2/GTMP2Large and G3(MP2)-RAD(+)) are directly carried out within the continuum model. Increasing the accuracy of the electronic structure theory may or may not improve the agreement with experiment suggesting that the error is largely in the solvation model. For amino acids where their gas and solution phase species exist as different tautomers, the direct approach provided a significant improvement in calculated pKas. These results demonstrate that direct calculation of solution phase pKas and reduction potentials within the SMD model provides a general and reliable approximation to corresponding thermodynamic cycle based protocols, and is recommended for systems where solvation induced changes in geometry are significant. Further studies are necessary to ascertain whether the results are generalisable to other continuum solvation models. PMID:25503399

  13. CO 2 reduction potentials by utilizing waste plastics in steel works

    Microsoft Academic Search

    Yu Sekine; Koichi Fukuda; Kenji Kato; Yoshihiro Adachi; Yasunari Matsuno

    2009-01-01

    Background, aim, and scope  Feedstock recycling has received attention as an effective method to recycle waste plastics. However, estimating the reduction\\u000a potential by life cycle assessment using coke oven and blast furnace in steel works has been a challenging task due to the\\u000a complex structure of energy flow in steel works. Municipal waste plastics consist of several plastic resins. Previous studies

  14. 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.

  15. Oxidation/Reduction Reactions Involving Dissolved Humics as Electron Shuttlers in Lake Sediments

    NASA Astrophysics Data System (ADS)

    McKnight, D. M.

    2005-12-01

    The chemical diversity of dissolved organic material (DOM) increases in aquatic ecosystems as the production of DOM by algae and bacteria contributes to DOM from runoff of soils and vegetation in forested catchments. Recent research has shown that a major DOM fraction, fulvic acid, can be used as electron acceptors by heterotrophic microorganisms in reducing environments and that reduced fulvic acid can in turn be used as an energy source by other microorganisms. The hydrologic transport of reduced DOM from reducing environments, such as lake sediments, to oxidizing environments may influence the mobility of iron and manganese in sediments, along with other trace metals sorbed on oxide phases. The electron shuttling properties of fulvic acids are associated with quinone moieties. One way in which fulvic acid from plant/soil and microbial sources differ is in the chemical characteristics of these quinone moieties. These differences, as well as the oxidation state of the quinones, can be characterized by fluorescence spectroscopy. In a study of an ice-covered lake in the Rocky Mountains, we found that as reduced fulvic acid accumulated in the water column, the concentration of ferrous iron also increased. When the ice-cover broke up in spring, the lake system rapidly oxidized and the iron was removed from solution, potentially deposited on the lake bottom as iron hydroxide. These quinone moieties differ in sensitive to oxidation and photolysis by light. Thus, the chemical diversity and biogeochemical reactivity of DOM in aquatic ecosystems are dynamic, with changes occurring over a day-night cycle being superimposed upon seasonal changes in hydrologic regime.

  16. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    PubMed

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode. PMID:25686380

  17. Phase formation in the process of iron and titanium oxides metallothermic reduction

    NASA Astrophysics Data System (ADS)

    Krasikov, S. A.; Nadolsky, A. L.; Shapovalov, A. G.; Pazdnikov, I. P.; Tashmurzin, A. Y.; Shurygin, Y. Y.; Osokina, M. A.

    2008-02-01

    Phase formation in the alloys obtained during process of collective Ti and Fe oxides reduction by Al has been investigated. Thermodynamic computer simulation of the process (based on the system free energy minimizing principle) has indicated a range of possible reactions with various metallic compounds formation. Differential-thermal (DT), X-ray diffraction (XRD) methods and melting of reaction mixtures at 1773-1973 K have been carried out to confirm the thermodynamic predictions. The DT experiments showed that the process began after Al melting at 943 K and was accompanied by large exothermic effects. The intermetallic phases of alloys with various content of Ti, Fe and Al have been observed by the XRD analysis.

  18. Reduction-oxidation poise regulates the sign of phototaxis in Chlamydomonas reinhardtii

    PubMed Central

    Wakabayashi, Ken-ichi; Misawa, Yuka; Mochiji, Shota; Kamiya, Ritsu

    2011-01-01

    In many phototrophic microorganisms and plants, chloroplasts change their positions relative to the incident light to achieve optimal photosynthesis. In the case of motile green algae, cells change their swimming direction by switching between positive and negative phototaxis, i.e., swimming toward or away from the light source, depending on environmental and internal conditions. However, little is known about the molecular signals that determine the phototactic direction. Using the green alga Chlamydomonas reinhardtii, we found that cellular reduction-oxidation (redox) poise plays a key role: Cells always exhibited positive phototaxis after treatment with reactive oxygen species (ROS) and always displayed negative phototaxis after treatment with ROS quenchers. The redox-dependent switching of the sign of phototaxis may contribute in turn to the maintenance of cellular redox homeostasis. PMID:21690384

  19. Synthesis of full-density nanocrystalline tungsten carbide by reduction of tungstic oxide at room temperature

    SciTech Connect

    El-Eskandarany, M.S.; Omori, M.; Ishikuro, M.; Konno, T.J.; Takada, K.; Sumiyama, K.; Hirai, T.; Suzuki, K. [Tohoku Univ., Sendai (Japan)

    1996-12-01

    Among the hard alloys, WC alloys find wide industrial applications as tips for cutting tools and wear-resistant parts. Their intrinsic resistance to oxidation and corrosion at high temperatures also makes them desirable as a protective coating for devices at elevated temperatures. In the industrial scale of production, WC is prepared by a direct union of the elements at a temperature of 3,273 to 3,473 K. Accordingly, the high cost of preparation is a disadvantage of this process. Here, the authors report a novel technique for preparing a large amount of WC powder using a simple method. This process is based on mechanical solid-state reduction (MSSR) followed y solid-state reaction (SSR) during room-temperature ball milling (a high energy ball mill, Fritsch P6, was used at a rotation speed of 4.2 s{sup {minus}1}) of a mixture of WO{sub 3}, Mg, and C powders.

  20. Nitrogen removal from wastewater using simultaneous nitrate reduction and anaerobic ammonium oxidation in single reactor.

    PubMed

    Sumino, Tatsuo; Isaka, Kazuichi; Ikuta, Hajime; Saiki, Yuko; Yokota, Toyokazu

    2006-10-01

    The effects of C/N ratio and total organic carbon (TOC) loading on nitrogen removal through simultaneous nitrate reduction and anaerobic ammonium oxidation in a single reactor were examined. Granular sludge taken from a methane fermentation reactor was placed in an upflow reactor and supplied with synthetic wastewater containing nitrate at a C/N ratio of 1 to grow heterotrophic denitrifying bacteria. When nitrogen removal ratio reached 30%, anammox sludge attached to nonwoven-carrier was added into the same reactor and then ammonia was added to the synthetic wastewater. Nitrogen removal ratio was markedly increased to 80-94%. In this system, nitrogen removal ratio was affected by C/N ratio and TOC loading, not by the amount of granular sludge. A stable isotopic analysis using 15N-labeled nitrate showed that N2 gas was formed by anammox reaction. PMID:17116583

  1. Mercury Oxidation Promoted by a Selective Catalytic Reduction Catalyst under Simulated Powder River Basin Coal Combustion Conditions

    Microsoft Academic Search

    Chun W. Lee; Shannon D. Serre; Yongxin Zhao; Sung Jun Lee; Thomas W. Hastings; Paul Chin; David Ollis; Jing Qian; Andrea Ferro; Kathleen Fowler; Hyukjin Oh; Kalyan Annamalai; John Sweeten; Jennifer Stokke; David Mazyck; James Corbett; James Winebrake; Lokman Tecer; Pinar ren; Omar Alagha; Ferhat Karaca; Sue Sheya; Clifford Glowacki; Ming-Chih Chang; Judith Chow; John Watson; Ching-Ho Lin; Edith Ge´go; Alice Gilliland; James Godowitch; S. Rao; P. Porter; Christian Hogrefe

    2008-01-01

    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 (Hg0) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride

  2. 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.

  3. 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).

  4. 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.

  5. 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

  6. Uncertainty assessment of spatially distributed nitrate reduction potential in groundwater using multiple geological realizations

    NASA Astrophysics Data System (ADS)

    Hansen, A. L.; Gunderman, D.; He, X.; Refsgaard, J. C.

    2014-11-01

    Spatially distributed nitrate reduction potential in groundwater was estimated for the clay till dominated Norsminde fjord catchment in Denmark using the distributed hydrological model MIKE SHE. The nitrate transport was simulated using particle tracking and nitrate was assumed to be instantaneously reduced at the redox interface. Spatially distributed depths of the redox interface were estimated based on the spatial patterns in groundwater recharge and sediment redox capacity. Uncertainty of the estimated nitrate reduction due to geological uncertainty was assessed using multiple geological realizations. The geological realizations were generated using the geostatistical software TProGS and either conditioned based on borehole data only or soft conditioned based on both borehole data and geophysical data. Finally an upscaling of the predicted nitrate reduction was done in order to evaluate the change in uncertainty with increasing scale. The study showed that the uncertainty (one standard deviation) of the estimated nitrate reduction potential (in percentage of nitrate input) on the original 100 m model scale was 25% if only using borehole data and 19% if combining the borehole data with geophysical data. The uncertainty on the model predictions decreased with increasing aggregation scale. The decrease in uncertainty was most apparent the first 500 m, where after the uncertainty started to level off. This scale corresponded well to the mean length of the sand units within the clay till. It is concluded that using geophysical data in combination with borehole data in generation of geological realizations can help decrease uncertainty on the estimated nitrate reduction and that the predictive capability of distributed models is constrained by the spatial resolution of key data such as geology.

  7. Simultaneous reduction of iron–sulfur protein and cytochrome bL during ubiquinol oxidation in cytochrome bc1 complex

    PubMed Central

    Zhu, Jian; Egawa, Tsuyoshi; Yeh, Syun-Ru; Yu, Linda; Yu, Chang-An

    2007-01-01

    The key step of the protonmotive Q-cycle mechanism of the cytochrome bc1 complex is the bifurcated oxidation of ubiquinol at the Qp site. It was postulated that the iron–sulfur protein (ISP) accepts the first electron from ubiquinol to generate ubisemiquinone anion to reduce bL. Because of the difficulty of following the reduction of ISP optically, direct evidence for the early involvement of ISP in ubiquinol oxidation is not available. Using the ultra-fast microfluidic mixer and the freeze-quenching device, coupled with EPR, we have been able to determine the presteady-state kinetics of ISP and cytochrome bL reduction by ubiquinol. The first-phase reduction of ISP starts as early as 100 ?s with a t1/2 of 250 ?s. A similar reduction kinetic is also observed for cytochrome bL, indicating a simultaneous reduction of both ISP and bL. These results are consistent with the fact that no ubisemiquinone was detected at the Qp site during oxidation of ubiquinol. Under the same conditions, by using stopped flow, the reduction rates of cytochromes bH and c1 were 403 s?1 (t1/2 1.7 ms) and 164 s?1 (t1/2 4.2 ms), respectively. PMID:17360398

  8. 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.

  9. Organometallic dimers: application to work-function reduction of conducting oxides.

    PubMed

    Giordano, Anthony J; Pulvirenti, Federico; Khan, Talha M; Fuentes-Hernandez, Canek; Moudgil, Karttikay; Delcamp, Jared H; Kippelen, Bernard; Barlow, Stephen; Marder, Seth R

    2015-02-25

    The dimers of pentamethyliridocene and ruthenium pentamethylcyclopentadienyl mesitylene, (IrCp*Cp)2 and (RuCp*mes)2, respectively, are shown here to be effective solution-processable reagents for lowering the work functions of electrode materials; this approach is compared to the use of solution-deposited films of ethoxylated poly(ethylenimine) (PEIE). The work functions of indium tin oxide (ITO), zinc oxide, and gold electrodes can be reduced to 3.3-3.4 eV by immersion in a toluene solution of (IrCp*Cp)2; these values are similar to those that can be obtained by spin-coating a thin layer of PEIE onto the electrodes. The work-function reductions achieved using (IrCp*Cp)2 are primarily attributable to the interface dipoles associated with the formation of submonolayers of IrCp*Cp(+) cations on negatively charged substrates, which in turn result from redox reactions between the dimer and the electrode. The electrical properties of C60 diodes with dimer-modified ITO cathodes are similar to those of analogous devices with PEIE-modified ITO cathodes. PMID:25685873

  10. Development of oxide dispersion strengthened ferritic steel prepared by chemical reduction and mechanical milling

    NASA Astrophysics Data System (ADS)

    Sun, Q. X.; Fang, Q. F.; Zhou, Y.; Xia, Y. P.; Zhang, T.; Wang, X. P.; Liu, C. S.

    2013-08-01

    The oxide dispersion strengthened ferritic steel with a nominal composition of Fe-14Cr-2W-0.5Ti-0.06Si-0.2V-0.1Mn-0.05Ta-0.03C-0.3Y2O3 (14Cr-ODS) was fabricated by sol-gel method in combination with hydrogen reduction, mechanical alloying (MA) and hot isostatic pressing (HIP) techniques. Pure Fe-1.5Y2O3 precursor was obtained by a sol-gel process and a reduction process at 650 °C for 3 h and pure 14Cr-ODS alloy powders were obtained from this precursor and the alloying metallic powders by mechanical alloying. The microstructure analysis investigated by transmission electron microscopy (TEM) and energy dispersive spectrometry (EDS) reveal that Y-Ti-O complexes and V-Ti-O complexes with a main particle size of 8 nm are formed in the 14Cr-ODS steel matrix. After HIP sintering the weight and the relative density of the compacted ingots are about 0.8 kg and 99.7%. The uniform elongation and ultimate tensile strength of the ODS steel obtained by HIP after annealing at 1100 °C for 5 h are about 13% and 840 MPa, respectively.

  11. 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

  12. Reducing Nitrous Oxide Emissions from US Row-Crop Agriculture through Nitrogen Fertilizer Management: Development of an Nitrous Oxide Emissions Reduction Protocol

    NASA Astrophysics Data System (ADS)

    Millar, N.; Robertson, G. P.; Grace, P. R.; Gehl, R.; Hoben, J.; Kahmark, K.; Bohm, S.

    2009-12-01

    Nitrous oxide (N2O) is the major greenhouse gas emitted by US agriculture. About 80% of N2O emissions emanate from N fertilizer application and other soil management activities, with cropland emissions alone greater than 1 Tg yr-1. Manipulating fertilizer N inputs is a readily accessible management tool for increasing crop N use efficiency with fertilizer N rate, a crucial parameter for estimating both yield and N2O emissions in row-crop systems. Quantification of the trade-offs between N2O emissions, crop yield and fertilizer N rate is essential for proposing strategies which optimize productivity at economically and environmentally favorable N rates. The relationship between fertilizer N rate and subsequent N2O emissions is typically assumed linear and insensitive to increasing N rate. However, recent field studies at producer sites in Michigan, in winter wheat and corn, using static and automated chamber systems suggest that a non-linear relationship is more applicable. Emissions of N2O were low at fertilizer N rates below or coincident to those, optimizing crop yield but, sharply increased thereafter. This threshold response to increasing fertilizer N rate in row-crop agriculture suggests a substantial decrease in N2O emissions could be achieved with moderate reductions in N rate and little or no yield penalty. Our data, in conjunction with a recently developed approach for determining economically profitable N application rates for optimized crop yield in a number of Midwest states, have potential to be incorporated into agricultural N2O emission reduction protocols and utilized in future projects suitable for inclusion in the burgeoning nutrient cap-and-trade markets. We will present results from our 2007-2009 field seasons and outline a protocol framework for reducing N2O emissions from row-crop agriculture in the US Midwest.

  13. Oxidative stress mechanisms and potential therapeutics in Alzheimer disease

    Microsoft Academic Search

    P. I. Moreira; S. L. Siedlak; G. Aliev; X. Zhu; A. D. Cash; M. A. Smith; G. Perry

    2005-01-01

    Summary. Oxidative damage of biological macromolecules is a hallmark of most neurodegenerative disorders such as Alzheimer, Parkinson and diffuse Lewy body diseases. Another important phenomenon involved in these disorders is the alteration of iron and copper homeostasis. Data from the literature support the involvement of metal homeostasis in mitochondrial dysfunction, protein alterations and nucleic acid damage which are relevant in

  14. 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...

  15. Greenhouse gas and air pollutant emission reduction potentials of renewable energy--case studies on photovoltaic and wind power introduction considering interactions among technologies in Taiwan.

    PubMed

    Kuo, Yu-Ming; Fukushima, Yasuhiro

    2009-03-01

    To achieve higher energy security and lower emission of greenhouse gases (GHGs) and pollutants, the development of renewable energy has attracted much attention in Taiwan. In addition to its contribution to the enhancement of reliable indigenous resources, the introduction of renewable energy such as photovoltaic (PV) and wind power systems reduces the emission of GHGs and air pollutants by substituting a part of the carbon- and pollutant-intensive power with power generated by methods that are cleaner and less carbon-intensive. To evaluate the reduction potentials, consequential changes in the operation of different types of existing power plants have to be taken into account. In this study, a linear mathematical programming model is constructed to simulate a power mix for a given power demand in a power market sharing a cost-minimization objective. By applying the model, the emission reduction potentials of capacity extension case studies, including the enhancement of PV and wind power introduction at different scales, were assessed. In particular, the consequences of power mix changes in carbon dioxide, nitrogen oxides, sulfur oxides, and particulates were discussed. Seasonally varying power demand levels, solar irradiation, and wind strength were taken into account. In this study, we have found that the synergetic reduction of carbon dioxide emission induced by PV and wind power introduction occurs under a certain level of additional installed capacity. Investigation of a greater variety of case studies on scenario development with emerging power sources becomes possible by applying the model developed in this study. PMID:19320274

  16. Potential distribution analysis of suspended-type metal-oxide surge arresters

    Microsoft Academic Search

    Jinliang He; Rong Zeng; Shuiming Chen; Zhicheng Guan

    2003-01-01

    Nonuniformity of potential distribution of metal-oxide (ZnO) surge arresters reduces service lifetime of the arresters. The metal-oxide surge arresters of polymer housings developed can be suspended in different places. A combined method of electrical field and electric circuit is proposed to analyze the potential distribution of the suspended arresters. The equivalent electric circuit is obtained from a charge simulation method

  17. Importance of chlorogenic acid on the oxidative potential of potato tubers of two German cultivars

    Microsoft Academic Search

    E. Delgado; M. I. Sulaiman; E. Pawelzik

    2001-01-01

    Summary  Two German cultivars differing in blackspot susceptibility were grown in pots in 1998 and 1999 under control and water stress\\u000a conditions. Blackspot susceptibility of the tubers was defined as oxidative potential. The effect of free tyrosine, cysteine,\\u000a phenylalanine, chlorogenic and ascorbic acid on the oxidative potential was analyzed. A high concentration of ascorbic acid\\u000a led to a decrease in the

  18. 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. 

  19. In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area

    Microsoft Academic Search

    Katja Nauhaus; Antje Boetius; Martin Kruger; Friedrich Widdel

    2002-01-01

    Summary Anaerobic oxidation of methane (AOM) and sulphate reduction were examined in sediment samples from a marine gas hydrate area (Hydrate Ridge, NE Pacific). The sediment contained high numbers of microbial consortia consisting of organisms that affi- liate with methanogenic archaea and with sulphate- reducing bacteria. Sediment samples incubated under strictly anoxic conditions in defined mineral medium (salinity as in

  20. 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 ...

  1. Multi-component Zirconia-Titania Mixed Oxides: Catalytic Materials with Unprecedented Performance in the Selective Catalytic Reduction of NOx

    E-print Network

    Paris-Sud XI, Université de

    -urea systems for automotive catalytic converters [3]. However, V-Ti based materials, even promoted with WMulti-component Zirconia-Titania Mixed Oxides: Catalytic Materials with Unprecedented Performance in the Selective Catalytic Reduction of NOx with NH3 after harsh hydrothermal ageing. Nathalie MARCOTTE1#, Bernard

  2. Spatial Separation of Photochemical Oxidation and Reduction Reactions on the Surface of Ferroelectric BaTiO3

    E-print Network

    Rohrer, Gregory S.

    LETTERS Spatial Separation of Photochemical Oxidation and Reduction Reactions on the Surface reaction products are deposited on the surface in patterns that correspond to the underlying ferroelectric and holes migrate to the solid surface, where they can participate in reactions with adsorbed species. One

  3. BEHAVIOR OF DDT, KEPONE, AND PERMETHRIN IN SEDIMENT-WATER SYSTEMS UNDER DIFFERENT OXIDATION-REDUCTION AND PH CONDITIONS

    EPA Science Inventory

    A study was conducted to determine the effects of pH and oxidation-reduction (redox) conditions of soil and sediment-water systems on the persistence of three insecticide compounds. Three pH levels, ranging from moderately acid to mildy alkaline, were studied for each compound. F...

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

    E-print Network

    Suni, Ian Ivar

    predicted by its Pourbaix diagram. Several research groups have proposed cathodic treatments prior to Cu to Cu or Ag electrodeposition,12-17 thereby enhancing nucleation and adhesion. However, these methodsImpedance Studies of Ru Oxide Reduction in Sulfuric Acid Pranav P. Sharma and Ian Ivar Suni

  5. The reduction of nitric oxide with nitrogen atoms generated from a low cost plasma generator

    SciTech Connect

    Streichsbier, M.; Edgar, B.L.; Dibble, R.W. [Univ. of California, Berkeley, CA (United States)

    1995-12-31

    A novel post-combustion technique to remove NO{sub x} from flue gases of stationary sources has been developed. This selective non-catalytic process employs a low cost, low-power plasma generator to dissociate molecular nitrogen (N{sub 2}) into nitrogen radicals. The so obtained nitrogen radicals act as reducing reagent in the reverse Zeldovich reaction N + NO = N{sub 2} + O. The reaction has no activation energy, thus the process works well at low temperatures. Experiments were performed using a slip stream of exhaust from a diesel engine. With a small scale prototype plasma gun an optimum of 88% NO{sub x} removal was achieved. Numerical investigation of the chemical kinetics predicts almost complete reduction under optimal conditions. The addition of ammonia to the plasma generator feedstock produced a counter effect and limited the NO{sub x} destruction to 12%. Pure ammonia plasma could not be obtained in the experimental prototype. The process is decoupled from the combustion source, so it has potential as a retrofit device. Unlike other selective and non-selective reduction schemes, the process does not require high temperatures, thus the plasma generator can be located far downstream of the combustion zone. Although the study focused mainly on stationary diesel engines, this technique has also potential application for many stationary and mobile sources.

  6. Soil oxidation-reduction in wetlands and its impact on plant functioning.

    PubMed

    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

  7. Role of cation interactions in the reduction process in plutonium-americium mixed oxides.

    PubMed

    Belin, Renaud C; Martin, Philippe M; Lechelle, Jacques; Reynaud, Muriel; Scheinost, Andreas C

    2013-03-18

    The oxygen to metal ratio (O/M) is directly related to oxygen potential, which strongly influences the sintering and irradiation performance of nuclear fuels. A better understanding of these two parameters is therefore of major interest. To further ascertain the correlation between O/M ratio and oxygen potential in Am-bearing MOX, several thermodynamic descriptions are being developed. Despite their differences, they all involve the valence of actinide cations (e.g., U, Pu, and Am) as essential parameters. However, as no experimental data on their valence are available, these models rely on assumptions. In the present work, we coupled X-ray diffraction and X-ray absorption spectroscopy to follow the behavior of Pu and Am in three hypo-stoichiometric, U-free Pu(1-y)Am(y)O(2-x) compounds. We provide for the first time a quantitative determination of Pu and Am valences, demonstrating that plutonium reduction from Pu(4+) to Pu(3+) starts only when americium reduction from Am(4+) to Am(3+) is completed. This result fills in an important gap in experimental data, thereby improving the thermodynamic description of nuclear fuels. At last, we suggest that the O/M ratio may evolve at room temperature, especially for high Am content, which is of main concern for the fabrication of Am-loaded MOX and their storage prior to irradiation. PMID:23441886

  8. The reduction and oxidation of cationic carbonyl complexes of manganese with phosphoniodithioformate: X-ray crystal structure of [Mn(CO) 4(S 2CPCy 3)]ClO 4

    Microsoft Academic Search

    Gabino A. Carriedo; Julio A. Pérez-Martínez; Daniel Miguel; Víctor Riera; Santiago García-Granda; Enrique Pérez-Carreño

    1996-01-01

    Manganese carbonyl complexes of the types behaviour have been studied by cyclic voltammetry and controlled potential electrolysis, showing that they undergo one-electron reduction and one-electron oxidation at potentials that depend mainly on the number of carbonyls. The results have been explained on the basis on an MO study at an EH level carried out on the model complexes [Mn(CO)4(S2CPH3)]+ (1b),

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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. [Praxair Inc., Tonawanda, NY (United States). Praxair Technological Center

    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.

  15. The performance of perovskites and spinels as catalysts for oxygen reduction in solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Martin, Boris E.

    The lack of understanding of the catalytic process at the state-of-the-art cathode material surface in solid oxide fuel cells, (La0.8Sr 0.2)0.98MnO3+delta (LSM), has hindered the design of better catalysts. The objectives of this study were to design a system enabling the comparison of catalytic activities of different cathode materials independently of morphological factors, as well as to resolve catalytic processes at the LSM surface. The selection and optimization of potential cathode materials were performed on the basis of thermal expansion, four-probe dc-conductivity and thermoelectric power measurements in air. The materials studied as potential cathodes were tungsten, niobium and molybdenum doped barium cobaltite perovskites, copper manganese, cobalt manganese and cobalt ferrite spinels as well as strontium doped lanthanum cobalt ferrites and lanthanum manganite perovskites. The doped barium cobaltites were found lo offer superior electrical conductivity when octahedral site transition metal average valence was mixed 3+ /4+ compared to mixed 2+/3+. On the other hand, the loss of conductivity associated with octahedral site doping rendered these materials inadequate for solid oxide fuel cells (SOFC) cathode applications. Copper manganese spMd was found to exhibit electrical conductivity as high as ˜200 S.cm-1 at 1073 K and thermal expansion ˜ 11 ppm/K between 298 K and 1200 K. Thermal and chrono-potentiometric studies were used to determine the oxygen diffusivity, in cobalt and strontium doped lanthanum iron perovskites (LSCF), and revealed that the activation of strontium doped lanthanum manganese perovskites (LSM) under cathodic bias is kinetically limited by its rate of oxygen surface exchange, suggesting that the cathodic activation of LSM is due to its change in oxygen content under bias. The electronic defect structure of the cubic spinels was resolved in a defect reaction model involving the thermally activated redox of Cu + and Mn4+ to Cu2+ and Mn3+, as well as the disproportionation of Jahn-Teller ion Mn3+ into Mn2+ and Mn4+ and demonstrated that copper doping enhanced the amount of Mn4+ on octahedral sites. Cyclic voltammetry and potential-dependent electrochemical impedance spectroscopy studies of dense (La0.8Sr0.2)0.98MnO3+delta polycrystalline films revealed that the rate determining step in the oxygen reduction reaction, in the conditions of our study was the first charge transfer between oxygen ad-atoms and octahedral manganese III, as described by (S)Oad + MnxMn?O -adS +Mn•Mn. The catalytic activity of CuzMn3-- zO4 cubic spinets was found superior to that of LSM and of stoichiometrie CoFe2O4 and Co2MnO 4 spinal at intermediate temperature, suggesting that the Mn 3+/Mn4+ redox couple on octahedral sites plays a major role in the catalysis of the oxygen reduction reaction on those transition metal oxide surfaces.

  16. Mechanism of Porcine Liver Xanthine Oxidoreductase Mediated N-Oxide Reduction of Cyadox as Revealed by Docking and Mutagenesis Studies

    PubMed Central

    Hao, Haihong; Dai, Menghong; Wang, Xu; Huang, Lingli; Liu, Zhenli; Yuan, Zonghui

    2013-01-01

    Xanthine oxidoreductase (XOR) is a cytoplasmic molybdenum-containing oxidoreductase, catalyzing both endogenous purines and exogenous compounds. It is suggested that XOR in porcine hepatocytes catalyzes the N-oxide reduction of quinoxaline 1,4-di-N-oxides (QdNOs). To elucidate the molecular mechanism underlying this metabolism, the cDNA of porcine XOR was cloned and heterologously expressed in Spodoptera frugiperda insect cells. The bovine XOR, showing sequence identity of 91% to porcine XOR, was employed as template for homology modeling. By docking cyadox, a representative compound of QdNOs, into porcine XOR model, eight amino acid residues, Gly47, Asn352, Ser360, Arg427, Asp430, Asp431, Ser1227 and Lys1230, were located at distances of less than 4Å to cyadox. Site-directed mutagenesis was performed to analyze their catalytic functions. Compared with wild type porcine XOR, G47A, S360P, D431A, S1227A, and K1230A displayed altered kinetic parameters in cyadox reduction, similarly to that in xanthine oxidation, indicating these mutations influenced electron-donating process of xanthine before subsequent electron transfer to cyadox to fulfill the N-oxide reduction. Differently, R427E and D430H, both located in the 424–434 loop, exhibited a much lower Km and a decreased Vmax respectively in cyadox reduction. Arg427 may be related to the substrate binding of porcine XOR to cyadox, and Asp430 is suggested to be involved in the transfer of electron to cyadox. This study initially reveals the possible catalytic mechanism of porcine XOR in cyadox metabolism, providing with novel insights into the structure-function relationship of XOR in the reduction of exogenous di-N-oxides. PMID:24040113

  17. Assessment of an ICA-based noise reduction method for multi-channel auditory evoked potentials

    NASA Astrophysics Data System (ADS)

    Mirahmadizoghi, Siavash; Bell, Steven; Simpson, David

    2015-03-01

    In this work a new independent component analysis (ICA) based method for noise reduction in evoked potentials is evaluated on for auditory late responses (ALR) captured with a 63-channel electroencephalogram (EEG) from 10 normal-hearing subjects. The performance of the new method is compared with a single channel alternative in terms of signal to noise ratio (SNR), the number of channels with an SNR above an empirically derived statistical critical value and an estimate of hearing threshold. The results show that the multichannel signal processing method can significantly enhance the quality of the signal and also detected hearing thresholds significantly lower than with the single channel alternative.

  18. A highly sensitive colorimetric microplate ferrocyanide assay applied to ascorbate-stimulated transplasma membrane ferricyanide reduction and mitochondrial succinate oxidation.

    PubMed

    Lane, Darius J R; Lawen, Alfons

    2008-02-15

    Ferricyanide reduction frequently is analyzed to determine the activity of membraneous reductases. An improved, highly sensitive, and rapid method for quantitative endpoint determination of ferrocyanide is presented. Ferrocyanide is oxidized by Fe(3+) in the presence of Ferene-S under acid conditions to form a chromogenic Ferene-S/Fe(2+) complex. The latter is quantitated at 593 nm with a sensitivity of 33.2 mM(-1) . cm(-1). The assay is 60% more sensitive to ferrocyanide (and with a 50% lower detection limit) than the prevailing method of Avron and Shavit, which employs sulfonated bathophenanthroline as the ferrous chromogen. Both pH dependence and potential sources of interference are discussed. Using the method, a sulfhydryl-sensitive, ascorbate-stimulated transplasma membrane ferricyanide reductase was assayed in human chronic myeloid (K562) leukemia cells. Furthermore, malonate-sensitive succinate dehydrogenase activity of heart mitochondria was easily assayed with ferricyanide as terminal electron acceptor. The current method will suit routine applications demanding high throughput, robustness, and sensitivity in a 96-well plate format. PMID:17949676

  19. Electrolytic Reduction of Spent Nuclear Oxide Fuel -- Effects of Fuel Form and Cathode Containment Materials on Bench-Scale Operations

    SciTech Connect

    S. D. Herrmann

    2007-09-01

    A collaborative effort between the Idaho National Laboratory (INL) and Korea Atomic Energy Research Institute (KAERI) is underway per an International Nuclear Energy Research Initiative to advance the development of a pyrochemical process for the treatment of spent nuclear oxide fuel. To assess the effects of specific process parameters that differ between oxide reduction operations at INL and KAERI, a series of 4 electrolytic reduction runs will be performed with a single salt loading of LiCl-Li2O at 650 °C using a test apparatus located inside of a hot cell at INL. The spent oxide fuel for the tests will be irradiated UO2 that has been subjected to a voloxidation process to form U3O8. The primary variables in the 4 electrolytic reduction runs will be fuel basket containment material and Li2O concentration in the LiCl salt. All 4 runs will be performed with comparable fuel loadings (approximately 50 g) and fuel compositions and will utilize a platinum anode and a Ni/NiO reference electrode. The first 2 runs will elucidate the effect of fuel form on the electrolytic reduction process by comparison of the above test results with U3O8 versus results from previous tests with UO2. The first 3 runs will investigate the impact that the cathode containment material has on the electrolytic reduction of spent oxide fuel. The 3rd and 4th runs will investigate the effect of Li2O concentration on the reduction process with a porous MgO cathode containment.

  20. The Effect of Copper Loading on the Selective Catalytic Reduction of Nitric Oxide by Ammonia Over Cu-SSZ-13

    SciTech Connect

    Kwak, Ja Hun; Tran, Diana N.; Szanyi, Janos; Peden, Charles HF; Lee, Jong H.

    2012-03-01

    The effect of Cu loading on the selective catalytic reduction of NOx by NH3 was examined over 20-80% ion-exchanged Cu-SSZ-13 zeolite catalysts. High NO reduction efficiency (80-95%) was obtained over all catalyst samples between 250 and 500°C, and the gas hourly space velocity of 200,000 h-1. Both NO reduction and NH3 oxidation activities under these conditions were found to increase slightly with increasing Cu loading at low temperatures. However, NO reduction activity was suppressed with increasing Cu loadings at high temperatures (>500oC) due to excess NH3 oxidation. The optimum Cu ion exchange level appears to be ~40-60% as higher than 80% NO reduction efficiency was obtained over 50% Cu ion-exchanged SSZ-13 up to 600oC. The NO oxidation activity of Cu-SSZ-13 was found to be low regardless of Cu loading, although it was somewhat improved with increasing Cu ion exchange level at high temperatures. During the “fast” SCR (i.e., NO/NO2 =1), only a slight improvement in NOx reduction activity was obtained for Cu-SSZ-13. Regardless of Cu loading, near 100% selectivity to N2 was observed; only a very small amount of N2O was produced even in the presence of NO2. Based on the Cu loading, the apparent activation energies for NO oxidation and NO SCR were estimated to be ~58 kJ/mol and ~41 kJ/mol, respectively.

  1. Electrochemical removal of bromide and reduction of THM formation potential in drinking water.

    PubMed

    Kimbrough, David Eugene; Suffet, I H

    2002-11-01

    Trihalomethanes (THMs), a by-product of the chlorination of natural waters containing dissolved organic carbon and bromide, are the focus of considerable public health concern and regulation due to their potential as a carcinogen by ingestion. This paper presents a promising new water treatment process that lowers the concentration of bromide in drinking water and thus, lowers the THM formation potential. Bromide is oxidized by electrolysis to bromine and then the bromine apparently volatilized. The electrolyzed water, when chlorinated, produces measurably lower amounts of THMs and proportionately fewer brominated THMs, which are of greater public health concern than the chlorinated THMs. Removing bromide should also reduce the formation of other disinfection by-products such as bromate and haloacetic acids. PMID:12448534

  2. 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

  3. Changing redox potential by controlling soil moisture and addition of inorganic oxidants to dissipate pentachlorophenol in different soils.

    PubMed

    Lin, Jiajiang; He, Yan; Xu, Jianming

    2012-11-01

    The potential for dissipation of pentachlorophenol (PCP) was investigated in soils from four different sites in China. These were an umbraqualf (Soil 1), a Plinthudult (Soil 2), a Haplustalf (Soil 3) and an Argiustoll (Soil 4) which were either flooded, to produce anaerobic conditions, or incubated aerobically at 60% water-holding capacity (WHC). The dissipation of PCP in Soil 1 at 60% WHC was higher than under flooded condition, while the opposite occurred in the other three soils. Under flooded conditions, the redox potential decreased significantly in Soil 1 and Soil 4, where sulphate reduction was occurred and the dissipation of PCP was statistically significant (about 96% and 98%, respectively) at the end of incubation. After addition of inorganic oxidants, dissipation of PCP was significantly inhibited by FeCl(3), while Na(2)SO(4) and NaNO(3) had different effects, depending upon the soil type. PMID:22842055

  4. The promoting role of rare earth oxides on Fe-exchanged TiO 2-pillared clay for selective catalytic reduction of nitric oxide by ammonia

    Microsoft Academic Search

    R. Q Long; R. T Yang

    2000-01-01

    Fe3+-exchanged TiO2-pillared clay (Fe–TiO2–PILC) has been previously found to be more active than vanadia-based catalysts for selective catalytic reduction (SCR) of NO by NH3. The promoting role of rare earth oxides with variable valence (i.e. CeO2, PrO1.83 and TbO1.75) on the Fe–TiO2–PILC was studied in this work. The catalysts were also characterized by XRD, FT-IR and NO oxidation experiments. It

  5. 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

  6. Superconductor/ferromagnet heterostructures exhibit potential for significant reduction of hysteretic losses

    NASA Astrophysics Data System (ADS)

    Krüger, Philipp; Grilli, Francesco; Vojen?iak, Michal; Zermeño, Victor M. R.; Demencik, Eduard; Farinon, Stefania

    2013-05-01

    First experimental observations of the ferromagnetic shielding effect in high-Tc superconducting coated conductors were carried out. Experimental results were compared to simulations calling upon finite-element calculations based on the H-formulation of Maxwell equations to model superconducting strips with ferromagnetic shields. Samples of copper-stabilized coated conductors were electroplated with nickel shields and afterwards characterized. Both externally applied oscillating transverse magnetic fields as well as transport currents were studied. Having observed promising gains with respect to the reduction of ac losses in both cases, we further investigated the potential of ferromagnetic shielding. The numerical model was able to reproduce and also predict experimental results very well and will serve as an indispensable tool to determine the potential of soft ferromagnetic materials to significantly reduce hysteretic losses.

  7. 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.

  8. Electrochemical oxidation of nitrite and the oxidation and reduction of NO2 in the room temperature ionic liquid [C2mim][NTf2].

    PubMed

    Broder, Tessa L; Silvester, Debbie S; Aldous, Leigh; Hardacre, Christopher; Compton, Richard G

    2007-07-12

    The electrochemical oxidation of potassium nitrite has been studied in the room temperature ionic liquid (RTIL) [C2mim][NTf2] by cyclic voltammetry at platinum electrodes. A chemically irreversible oxidation peak was observed, and a solubility of 7.5(+/-0.5) mM and diffusion coefficient of 2.0(+/-0.2)x10(-11) m2 s(-1) were calculated from potential step chronoamperometry on the microdisk electrode. A second, and sometimes third, oxidation peak was also observed when the anodic limit was extended, and these were provisionally assigned to the oxidation of nitrogen dioxide (NO2) and nitrate (NO3-), respectively. The electrochemical oxidation of nitrogen dioxide gas (NO2) was also studied by cyclic voltammetry in [C2mim][NTf2] on Pt electrodes of various size, giving a solubility of ca. 51(+/-0.2) mM and diffusion coefficient of 1.6(+/-0.05)x10(-10) m2 s(-1) (at 25 degrees C). It is likely that NO2 exists predominantly as its dimer, N2O4, at room temperature. The oxidation mechanism follows a CE process, which involves the initial dissociation of the dimer to the monomer, followed by a one-electron oxidation. A second, larger oxidation peak was observed at more positive potentials and is thought to be the direct oxidation of N2O4. In addition to understanding the mechanisms of NO2- and NO2 oxidations, this work has implications in the electrochemical detection of nitrite ions and of NO2 gas in RTIL media, the latter which may be of particular use in gas sensing. PMID:17571880

  9. Advanced oxidation and reduction processes: Closed-loop applications for mixed waste

    SciTech Connect

    Coogan, J.J.; Tennant, R.A.; Rosocha, L.A.; Wantuck, P.J.

    1993-05-01

    At Los Alamos we are engaged in applying innovative oxidation and reduction technologies to the destruction of hazardous organics. Non thermal plasmas and relativistic electron-beams both involve the generation of free radicals and are applicable to a wide variety of mixed waste as closed-loop designs can be easily engineered. Silent discharge plasmas (SDP), long used for the generation of ozone, have been demonstrated in the laboratory to be effective in destroying hazardous organic compounds and offer an altemative to existing post-incineration and off-gas treatments. SDP generates very energetic electrons which efficiently create reactive free radicals, without adding the enthalpy associated with very high gas temperatures. A SDP cell has been used as a second stage to a LANL designed, packed-bed reactor (PBR) and has demonstrated DREs as high as 99.9999% for a variety of combustible liquid and gas-based waste streams containing scintillation fluids, nitrates, PCB surrogates, and both chlorinated and fluorinated solvents. Radiolytic treatment of waste using electron-beams and/or bremsstrahlung can be applied to a wide range of waste media (liquids, sludges, and solids). The efficacy and economy of these systems has been demonstrated for aqueous waste through both laboratory and pilot scale studies. We win present recent experimental and theoretical results for systems using stand alone SDP, combined PBR/SDP, and electron-beam treatment methods.

  10. Advanced oxidation and reduction processes: Closed-loop applications for mixed waste

    SciTech Connect

    Coogan, J.J.; Tennant, R.A.; Rosocha, L.A.; Wantuck, P.J.

    1993-01-01

    At Los Alamos we are engaged in applying innovative oxidation and reduction technologies to the destruction of hazardous organics. Non thermal plasmas and relativistic electron-beams both involve the generation of free radicals and are applicable to a wide variety of mixed waste as closed-loop designs can be easily engineered. Silent discharge plasmas (SDP), long used for the generation of ozone, have been demonstrated in the laboratory to be effective in destroying hazardous organic compounds and offer an altemative to existing post-incineration and off-gas treatments. SDP generates very energetic electrons which efficiently create reactive free radicals, without adding the enthalpy associated with very high gas temperatures. A SDP cell has been used as a second stage to a LANL designed, packed-bed reactor (PBR) and has demonstrated DREs as high as 99.9999% for a variety of combustible liquid and gas-based waste streams containing scintillation fluids, nitrates, PCB surrogates, and both chlorinated and fluorinated solvents. Radiolytic treatment of waste using electron-beams and/or bremsstrahlung can be applied to a wide range of waste media (liquids, sludges, and solids). The efficacy and economy of these systems has been demonstrated for aqueous waste through both laboratory and pilot scale studies. We win present recent experimental and theoretical results for systems using stand alone SDP, combined PBR/SDP, and electron-beam treatment methods.

  11. 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.

  12. Effect of alkaline earth oxides on the formation of surface microphases that protect strontium titanate from reduction

    SciTech Connect

    Aksenova, L.A.; Kostikov, Yu.P.; Leonov, A.I.; Rotenberg, B.A.; Strykanov, V.S.

    1986-08-20

    The authors studied the effect of addition of strontium oxide, barium oxide, and calcium oxide on the formation of surface microphases and the reduction of strontium titanate. The materials were strontium carbonate, barium carbonate, and calcium carbonate (analytical grade) and titanium dioxide (pure grade). X-ray diffraction analysis was carried out on a DRON-2.0 diffractometer (CuK/sub ..cap alpha../, Ni filter). The surface layers were studies in an electron spectrometer by ESCA (exciting irradiation Al/sub K..cap alpha../; bond energy in standard gold sample Au/sub 4/f/sub 1/2/ = 84.1 eV; depth of layer 8 nm). Samplers were prepared according to the usual ceramic technology. It was found that protection from reduction of strontium titanate that is doped with calcium, strontium, or barium oxide is related to the formation of surface microphases that are close to M/sub 2/TiO/sub 4/ in composition and do not undergo reduction when calcined in a medium at low partial pressure of oxygen.

  13. Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions.

    PubMed

    Lee, Chun W; Serre, Shannon D; Zhao, Yongxin; Lee, Sung Jun; Hastings, Thomas W

    2008-04-01

    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 (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas. PMID:18422035

  14. 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.

  15. 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

  16. Electronically conducting proton exchange polymers as catalyst supports for proton exchange membrane fuel cells. Electrocatalysis of oxygen reduction, hydrogen oxidation, and methanol oxidation

    SciTech Connect

    Lefebvre, M.C.; Qi, Z.; Pickup, P.G. [Memorial Univ. of Newfoundland, St. John`s, Newfoundland (Canada). Dept. of Chemistry] [Memorial Univ. of Newfoundland, St. John`s, Newfoundland (Canada). Dept. of Chemistry

    1999-06-01

    A variety of supported catalysts were prepared by the chemical deposition of Pt and Pt-Ru particles on chemically prepared poly(3,4-ethylenedioxythiophene)/poly(styrene-4-sulfonate) (PEDOT/PSS) and PEDOT/polyvinylsulfate (PVS) composites. The polymer particles were designed to provide a porous, proton-conducting and electron-conducting catalyst support for use in fuel cells. These polymer-supported catalysts were characterized by electron microscopy, impedance spectroscopy, cyclic voltammetry, and conductivity measurements. Their catalytic activities toward hydrogen and methanol oxidation and oxygen reduction were evaluated in proton exchange membrane fuel-cell-type gas diffusion electrodes. Activities for oxygen reduction comparable to that obtained with a commercial carbon-supported catalyst were observed, whereas those for hydrogen and methanol oxidation were significantly inferior, although still high for prototype catalysts.

  17. ChemTeacher: Electric Potential

    NSDL National Science Digital Library

    2011-01-01

    ChemTeacher compiles background information, videos, articles, demonstrations, worksheets and activities for high school teachers to use in their classrooms. The Electric Potential page includes resources for teaching students about calculating standard electrode potentials for oxidation-reduction reactions.

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

    PubMed

    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

  19. 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

  20. Reduction of Uranium(VI) under Sulfate-reducing Conditions in the Presence of Fe(III)-(hydr)oxides

    SciTech Connect

    Sani, Rajesh K.; Peyton, Brent M.; Amonette, James E.; Geesey, Gill G.

    2004-06-01

    U(VI) dissolved in a modified lactate-C medium (either sulfate- or lactate-limited) was reacted with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz under anoxic conditions and equivalent mineral surface areas. After sorption equilibration, the suspensions were inoculated with a sulfate-reducing bacterium (SRB, Desulfovibrio desulfuricans G20). Inoculation of the suspensions containing sulfate-limited medium yielded significant SRB growth, along with concomitant reduction of sulfate and removal of U(VI) from solution. Inoculation of the suspensions containing lactate-limited medium yielded similar results while lactate was still present. Once the lactate was depleted, however, some of the U that had been removed from solution was re-solubilized in the hematite treatment and, to a lesser extent, in the goethite treatment. No re-solubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of four months. Analysis by U L3-edge XANES spectroscopy of mineral specimens sampled without inoculation yielded a typical U(VI) spectrum. Mineral specimens sampled at the end of the experiment yielded spectra similar to that of uraninite, thus providing strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, U re-solubilization was attributed to re-oxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Our results thus suggest that inoculation with SRB mediates reduction of soluble U(VI) to an insoluble U(IV) oxide so long as a suitable electron donor is available. Depletion of the electron donor may result in partial re-oxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III) (hydr)oxides are incompletely reduced by reaction with SRB-generated sulfide.

  1. Parameterizing soil emission and atmospheric oxidation-reduction in a model of the global biogeochemical cycle of mercury.

    PubMed

    Kikuchi, Tetsuro; Ikemoto, Hisatoshi; Takahashi, Katsuyuki; Hasome, Hisashi; Ueda, Hiromasa

    2013-01-01

    Using the GEOS-Chem atmosphere-land-ocean coupled mercury model, we studied the significances of two processes, soil emission and atmospheric oxidation-reduction, in the global biogeochemical cycling of mercury and their parametrization to improve model performance. Implementing an empirical equation for soil emission flux (Esoil) including soil mercury concentration, solar radiation, and surface air temperature as parameters enabled the model to reproduce the observed seasonal variations of Esoil, whereas the default setting, which uses only the former two parameters, failed. The modified setting of Esoil also increased the model-simulated atmospheric concentration in the summertime surface layer of the lower- and midlatitudes and improved the model reproducibility for the observations in Japan and U.S. in the same period. Implementing oxidation of atmospheric gaseous elemental mercury (Hg(0)) by ozone with an updated rate constant, as well as the oxidation by bromine atoms (Br) in the default setting, improved the model reproducibility for the dry deposition fluxes observed in Japan. This setting, however, failed to reproduce the observed seasonal variations of atmospheric concentrations in the Arctic sites due to the imbalance between oxidation and reduction, whereas the model with Br as the sole Hg(0) oxidant in the polar atmosphere could capture the variations. PMID:24053722

  2. Siderophore-fluoroquinolone conjugates containing potential reduction-triggered linkers for drug release: synthesis and antibacterial activity.

    PubMed

    Ji, Cheng; Miller, Marvin J

    2015-06-01

    Syntheses of two Siderophore-fluoroquinolone conjugates with a potential reduction triggered linker for drug release are described. The "trimethyl lock" based linker incorporated in the conjugates was designed to be activated by taking advantage of the reductive pathway of bacterial iron metabolism. Electrochemical and LC-MS studies indicated that the linker is thermodynamically reducible by common biological reductants and the expected lactonization proceeds rapidly with concomitant release of the drug. Antibacterial activity assays revealed that conjugates with the reduction-triggered linker were more potent than their counterparts with a stable linker, which suggests that drug release occurs inside bacterial cells. PMID:25663417

  3. Neutralization potential determination of siderite (FeCO3) using selected oxidants.

    PubMed

    Haney, E B; Haney, R L; Hossner, L R; White, G N

    2006-01-01

    Siderite (FeCO3) is commonly found in coal overburden and, when present, can cause interference in the determination of neutralization potential (NP). Under acidic testing conditions, FeCO3 reacts to neutralize acid, which contributes to the NP. However, continued weathering of FeCO3 (oxidation of Fe2+ and hydrolysis of Fe3+) produces a neutral to slightly acidic solution. The effects of hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and O2 on the laboratory measurement of NP of siderite samples taken from overburden were examined. All oxidation treatments lowered the NP values of the siderite samples as compared with the standard USEPA method. However, oxidation with H2O2 produced variable results depending on the amount of H2O2 added. Neutralization potential values obtained after oxidation treatments were highly correlated with Mn concentration. Reaction products (i.e., 2-line ferrihydrite) of siderite samples with H2O2 and KMnO4 were not representative of natural siderite weathering. Oxidation with O2 produced the lowest NP values for siderite samples. The reaction products produced by oxidation with O2 most closely represent those intermediate products formed when siderite is exposed to atmospheric weathering conditions. Oxidation with O2 also proved to be the most reproducible method for accurately assessing NP when siderite is present in overburden samples. PMID:16641324

  4. 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.

  5. 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.

  6. Acetate Oxidation Coupled to Fe(III) Reduction in Hyperthermophilic Microorganisms

    Microsoft Academic Search

    JASON M. TOR; KAZEM KASHEFI; DEREK R. LOVLEY

    2001-01-01

    No hyperthermophilic microorganisms have previously been shown to anaerobically oxidize acetate, the key extracellular intermediate in the anaerobic oxidation of organic matter. Here we report that two hyperther- mophiles, Ferroglobus placidus and \\

  7. 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

  8. 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

  9. Cement replacement by sugar cane bagasse ash: CO2 emissions reduction and potential for carbon credits.

    PubMed

    Fairbairn, Eduardo M R; Americano, Branca B; Cordeiro, Guilherme C; Paula, Thiago P; Toledo Filho, Romildo D; Silvoso, Marcos M

    2010-09-01

    This paper presents a study of cement replacement by sugar cane bagasse ash (SCBA) in industrial scale aiming to reduce the CO(2) emissions into the atmosphere. SCBA is a by-product of the sugar/ethanol agro-industry abundantly available in some regions of the world and has cementitious properties indicating that it can be used together with cement. Recent comprehensive research developed at the Federal University of Rio de Janeiro/Brazil has demonstrated that SCBA maintains, or even improves, the mechanical and durability properties of cement-based materials such as mortars and concretes. Brazil is the world's largest sugar cane producer and being a developing country can claim carbon credits. A simulation was carried out to estimate the potential of CO(2) emission reductions and the viability to issue certified emission reduction (CER) credits. The simulation was developed within the framework of the methodology established by the United Nations Framework Convention on Climate Change (UNFCCC) for the Clean Development Mechanism (CDM). The State of São Paulo (Brazil) was chosen for this case study because it concentrates about 60% of the national sugar cane and ash production together with an important concentration of cement factories. Since one of the key variables to estimate the CO(2) emissions is the average distance between sugar cane/ethanol factories and the cement plants, a genetic algorithm was developed to solve this optimization problem. The results indicated that SCBA blended cement reduces CO(2) emissions, which qualifies this product for CDM projects. PMID:20493626

  10. Web-based computational chemistry education with CHARMMing III: Reduction potentials of electron transfer proteins.

    PubMed

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

    2014-07-01

    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

  11. CO{sub 2} reduction reactions in heterogeneous oxidation and catalytic cracking processes

    SciTech Connect

    Mamedov, Ag.Kh. [Institute Petrochemical Processes, Baku (Azerbaijan)

    1996-12-31

    The paper contains the results of heterogeneous catalytic activation of CO{sub 2} by various organic substances, generalizes main scientific aspects of the new direction {open_quotes}Oxidative Catalysis by Carbon Dioxide{close_quotes} and develop the petrochemical oxidative processes using carbon dioxide as an oxidant.

  12. In vitro toxicity of particulate matter (PM) collected at different sites in the Netherlands is associated with PM composition, size fraction and oxidative potential - the RAPTES project

    PubMed Central

    2011-01-01

    Background Ambient particulate matter (PM) exposure is associated with respiratory and cardiovascular morbidity and mortality. To what extent such effects are different for PM obtained from different sources or locations is still unclear. This study investigated the in vitro toxicity of ambient PM collected at different sites in the Netherlands in relation to PM composition and oxidative potential. Method PM was sampled at eight sites: three traffic sites, an underground train station, as well as a harbor, farm, steelworks, and urban background location. Coarse (2.5-10 ?m), fine (< 2.5 ?m) and quasi ultrafine PM (qUF; < 0.18 ?m) were sampled at each site. Murine macrophages (RAW 264.7 cells) were exposed to increasing concentrations of PM from these sites (6.25-12.5-25-50-100 ?g/ml; corresponding to 3.68-58.8 ?g/cm2). Following overnight incubation, MTT-reduction activity (a measure of metabolic activity) and the release of pro-inflammatory markers (Tumor Necrosis Factor-alpha, TNF-?; Interleukin-6, IL-6; Macrophage Inflammatory Protein-2, MIP-2) were measured. The oxidative potential and the endotoxin content of each PM sample were determined in a DTT- and LAL-assay respectively. Multiple linear regression was used to assess the relationship between the cellular responses and PM characteristics: concentration, site, size fraction, oxidative potential and endotoxin content. Results Most PM samples induced a concentration-dependent decrease in MTT-reduction activity and an increase in pro-inflammatory markers with the exception of the urban background and stop & go traffic samples. Fine and qUF samples of traffic locations, characterized by a high concentration of elemental and organic carbon, induced the highest pro-inflammatory activity. The pro-inflammatory response to coarse samples was associated with the endotoxin level, which was found to increase dramatically during a three-day sample concentration procedure in the laboratory. The underground samples, characterized by a high content of transition metals, showed the largest decrease in MTT-reduction activity. PM size fraction was not related to MTT-reduction activity, whereas there was a statistically significant difference in pro-inflammatory activity between Fine and qUF PM. Furthermore, there was a statistically significant negative association between PM oxidative potential and MTT-reduction activity. Conclusion The response of RAW264.7 cells to ambient PM was markedly different using samples collected at various sites in the Netherlands that differed in their local PM emission sources. Our results are in support of other investigations showing that the chemical composition as well as oxidative potential are determinants of PM induced toxicity in vitro. PMID:21888644

  13. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    PubMed

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media. PMID:25825826

  14. HYDROGEN-BASED, HOLLOW-FIBER MEMBRANE BIOFILM REACTOR FOR REDUCTION OF PERCHLORATE AND OTHER OXIDIZED CONTAMINANTS

    Microsoft Academic Search

    R. Nerenberg; B. E. Rittmann

    2004-01-01

    Many oxidized pollutants, such as nitrate, perchlorate, bromate, and chlorinated solvents, can be microbially reduced to less toxic or less soluble forms. For drinking water treatment, an electron donor must be added. Hydrogen is an ideal electron donor, as it is non-toxic, inexpensive, and sparsely soluble. We tested a hydrogen-based, hollow-fiber membrane biofilm reactor (MBfR) for reduction of perchlorate, bromate,

  15. A highly sensitive colorimetric microplate ferrocyanide assay applied to ascorbate-stimulated transplasma membrane ferricyanide reduction and mitochondrial succinate oxidation

    Microsoft Academic Search

    Alfons Lawen

    2008-01-01

    Ferricyanide reduction frequently is analyzed to determine the activity of membraneous reductases. An improved, highly sensitive, and rapid method for quantitative endpoint determination of ferrocyanide is presented. Ferrocyanide is oxidized by Fe3+ in the presence of Ferene-S under acid conditions to form a chromogenic Ferene-S\\/Fe2+ complex. The latter is quantitated at 593 nm with a sensitivity of 33.2 mM?1 ·

  16. 30S ribosomal proteins cross-linked to 16S RNA by periodate oxidation followed by borohydride reduction

    Microsoft Academic Search

    Jutta Rinke; Richard Brimacombe

    1978-01-01

    Gel electrophoretic techniques have been used to reexamine the RNA-protein cross-linking reaction induced by periodate oxidation and borohydride reduction of 30S ribosomal subunits. The results show that a number of 30S ribosomal proteins become attached to intact 16S RNA by this method, in addition to those already published. It follows that this cross-linking technique as it stands is of little

  17. Photoinduced reductive perfluoroalkylation of phosphine oxides: synthesis of P-perfluoroalkylated phosphines using TMDPO and perfluoroalkyl iodides.

    PubMed

    Sato, Yuki; Kawaguchi, Shin-Ichi; Ogawa, Akiya

    2015-06-16

    A photoinduced reaction between TMDPO (diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide) and perfluoroalkyl iodides successfully affords P-(perfluoroalkyl)diphenylphosphines as promising ligands for recyclable catalysts. Interestingly, the perfluoroalkylation reaction involves the reduction of phosphorus(v) compounds to phosphorus(iii) species. The advantages of the present reaction include the use of an air-stable phosphorus source and good yields of P-perfluoroalkylphosphines in short reaction times. PMID:26041689

  18. The kinetics of the oxidation-reduction reaction between uranium(VI) and titanium(III) in HCl solution

    Microsoft Academic Search

    Muhammad Abdul Hamid; Ejaz Ur Rehman; Muhammad Fuzail; Riffat Naheed; Amin-Uddin Ahmed

    1995-01-01

    The oxidation-reduction reaction between U(VI) and Ti(III) in HCl solution was studied spectrophotometrically. The reaction is second-order at all concentrations of reactants, HCl, ferrous chloride and mannitol used in this work. In 5M HCl the rate constantk increases with increasing Ti(III) concentration, whereas it decreases with increasing U(VI) concentration, with increasing HCl concentration from 1.00M to 7.17M and increases thereafter

  19. Cerium-terbium mixed oxides as potential materials for anodes in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Martínez-Arias, A.; Hungría, A. B.; Fernández-García, M.; Iglesias-Juez, A.; Conesa, J. C.; Mather, G. C.; Munuera, G.

    Highly homogeneous (Ce,Tb) oxides are prepared by a microemulsion technique, and their structural and electronic state after high temperature calcination is examined with X-ray diffraction, high resolution transmission electron microscopy, X-ray photoelectron and absorption (XANES) spectroscopies and impedance spectroscopy measurements. Addition of Tb stabilizes significantly (in comparison to pure ceria) specific surface area and small particles sizes during high temperature calcination (up to 1100 °C); phase decomposition at these high temperatures, similar to that occurring when stabilization of ceria is carried out with Zr, does not occur, and the mixed oxide remains homogeneous throughout. Tb addition to ceria may thus be beneficial when used as a component of SOFC anodes. TEM data indicate reshaping of oxide particles and provide evidence of crystal superstructures after high temperature treatments, while XPS and XANES reveal an increase in the Tb 4+/Tb 3+ ratio (for a given pretreatment) with the Tb/Ce ratio; Ce seems to be less reducible to Ce 3+ in the presence of Tb. Total electrical conductivity of CT samples under H 2 is mediated by electron transport (involving probably only Ce) and is lower than in gadolinia-doped ceria (GCO); in air conductivity is higher than for GCO, particularly at low temperatures, and it is probable that a p-type transport mechanism predominates in this case.

  20. Hydrogen-based, hollow-fiber membrane biofilm reactor for reduction of perchlorate and other oxidized

    E-print Network

    Nerenberg, Robert

    Hydrogen-based, hollow-fiber membrane biofilm reactor for reduction of perchlorate and other biofilm reactor (MBfR) for reduction of perchlorate, bromate, chlorate, chlorite, chromate, selenate Biofilm reactor; denitrification; hollow-fiber membrane; hydrogen; secondary substrate Introduction

  1. Nitric oxide potentiation of the homomeric ?1 GABAC receptor function

    PubMed Central

    Gasulla, J; Beltrán González, AN; Calvo, DJ

    2012-01-01

    BACKGROUND AND PURPOSE NO is a highly diffusible and reactive gas produced in the nervous system, which acts as a neuronal signal mediating physiological or pathological mechanisms. NO can modulate the activity of neurotransmitter receptors and ion channels, including NMDA and GABAA receptors. In the present work, we examined whether GABAC receptor function can also be regulated by NO. EXPERIMENTAL APPROACH Homomeric ?1 GABAC receptors were expressed in oocytes and GABA-evoked responses electrophysiologically recorded in the presence or absence of the NO donor DEA. Chemical protection of cysteines by selective sulfhydryl reagents and site-directed mutagenesis were used to determine the protein residues involved in the actions of NO. KEY RESULTS GABA?1 receptor responses were significantly enhanced in a dose-dependent, fast and reversible manner by DEA and the specific NO scavenger CPTIO prevented these potentiating effects. The ?1 subunits contain only three cysteine residues, two extracellular at the Cys-loop (C177 and C191) and one intracellular (C364). Mutations of C177 and C191 render the ?1 GABA receptors non-functional, but C364 can be safely exchanged by alanine (C364A). NEM, N-ethyl maleimide and (2-aminoethyl) methanethiosulfonate prevented the effects of DEA on GABA?1 receptors. Meanwhile, the potentiating effects of DEA on mutant GABA?1C364A receptors were similar to those observed on wild-type receptors. CONCLUSIONS AND IMPLICATIONS Our results suggest that the function of GABAC receptors can be enhanced by NO acting at the extracellular Cys-loop. PMID:22747884

  2. REDUCTION KINETICS OF MANGANESE OXIDE FROM HC FeMn SLAGS

    Microsoft Academic Search

    G. Tranell; S. Gaal; D. Lu; M. Tangstad; J. Safarian

    The kinetics of MnO reduction from high carbon ferromanganese slag was investigated using a sessile drop technique at 1600 ºC. The effects of reductant type, ambient atmosphere and slag composition on the MnO reduction were illuminated. Two different types of industrial reductants (ground to a particle size of 44 to 106 micron and pressed to pellets) were used as substrates

  3. Control of sulfidogenesis through bio-oxidation of H2S coupled to (per)chlorate reduction.

    PubMed

    Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G; Metlagel, Zoltan; Csencsits, Roseann; Auer, Manfred; Conrad, Mark E; Thieme, Jürgen; Northrup, Paul; Coates, John D

    2014-12-01

    We investigated H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. Based on our results, we propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments. PMID:25756108

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

    NASA Astrophysics Data System (ADS)

    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 (eg) 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 O22-/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.

  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. DRIFT study of CuO-CeO?-TiO? mixed oxides for NOx reduction with NH? at low temperatures.

    PubMed

    Chen, Lei; Si, Zhichun; Wu, Xiaodong; Weng, Duan

    2014-06-11

    A CuO-CeO2-TiO2 catalyst for selective catalytic reduction of NOx with NH3 (NH3-SCR) at low temperatures was prepared by a sol-gel method and characterized by X-ray diffraction, Brunner-Emmett-Teller surface area, ultraviolet-visible spectroscopy, H2 temperature-programmed reduction, scanning electron microscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). The CuO-CeO2-TiO2 ternary oxide catalyst shows excellent NH3-SCR activity in a low-temperature range of 150-250 °C. Lewis acid sites generated from Cu(2+) are the main active sites for ammonia activation at low temperature, which is crucial for low temperature NH3-SCR activity. The introduction of ceria results in increased reducibility of CuO species and strong interactions between CuO particles with the matrix. The interactions between copper, cerium and titanium oxides lead to high dispersion of metal oxides with increased active oxygen and enhanced catalyst acidity. Homogeneously mixed metal oxides facilitate the "fast SCR" reaction among Cu(2+)-NO, nitrate (coordinated on cerium sites) and ammonia (on titanium sites) on the CuO-CeO2-TiO2 catalyst at low temperatures. PMID:24848157

  7. Preparation and characterizations of BiVO?/reduced graphene oxide nanocomposites with higher visible light reduction activities.

    PubMed

    Wang, Aolan; Shen, Song; Zhao, Yibo; Wu, Wei

    2015-05-01

    Bismuth vanadate/reduced graphene oxide (BiVO4/RGO) composites were synthesized by one-step hydrothermal method with graphite oxide, Bi(NO3)3 and NH4VO3 as precursors. The as-synthesized nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, UV-Vis spectroscopy (UV), fluorescence spectroscopy (FL) and electrochemical impedance spectroscopy (EIS). The reduced graphene oxide sheets were decorated by butterfly-like BiVO4 lamellas. Such combination not only alleviated the agglomeration of BiVO4 particles but also restrained the restacking of reduced graphene oxide. A preliminary study on the photo-reductions of Cr (VI) and CO2 under the illumination of simulated sunlight with as-synthesized BiVO4/RGO nanocomposites as catalyst was carried out. The nanocomposites showed better photo-catalytic activity than the conventional BiVO4 particles. The photo-reduction efficiency of BiVO4/RGO nanocomposites increased about 50.1% and the ethanol yield improved about 15.4 ?mol/g-cat comparing with pure BiVO4. The enhancements of the photo-catalytic activities were attributed to the effective charge transfer of photo-generated electron from BiVO4 to RGO and improved absorption performance. PMID:25643960

  8. Efficient reduction of graphene oxide nanosheets using Na2C2O4 as a reducing agent

    NASA Astrophysics Data System (ADS)

    Hanifah, Mohamad Fahrul Radzi; Jaafar, Juhana; Aziz, Madzlan; Ismail, A. F.; Othman, M. H. D.; Rahman, Mukhlis A.; Norddin, M. N. A. M.; Yusof, N.; Salleh, W. N. W.

    2015-12-01

    The efficient synthesis of reduced graphene oxide (RGO) nanosheets via chemical reduction process of exfoliated graphene oxide (GO) nanosheets was performed by introducing sodium oxalate (Na2C2O4) as a reducing agent. To study the effects of the reduction time on the synthesized RGO, the GO was reduced within -1/2, 1 and 2 h for RGO-1, RGO-2 and RGO-3, respectively. The C/O atomic ratio of the synthesized RGO-3 has increased from 2.16 to 6.32 after reduction as determined by X-ray photoelectron spectroscopy (XPS). The morphology analysis of the RGO-3 was determined by high-resolution transmission electron microscopy (HRTEM) almost revealed the formation of single layer. The number of RGO layers decreases as the time of the reduction increases. Based on these analysis results, sodium oxalate plays an important role in the efficient removal of the oxygen containing groups in the GO to produce high quality of RGO.

  9. Comment on "New Insights in the Electrocatalytic Proton Reduction and Hydrogen Oxidation by Bioinspired Catalysts: A DFT Investigation"

    SciTech Connect

    Dupuis, Michel; Chen, Shentan; Raugei, Simone; DuBois, Daniel L; Bullock, R. Morris

    2011-05-12

    In the title paper, Vetere et al. reported a computational investigation of the mechanism of H{sub 2} oxidation/proton reduction using a model of nickel-based electrocatalysts that incorporates pendant amines in cyclic phosphorus ligands. These catalysts are attracting considerable attention owing to their high turnover rates and relatively low overpotentials. These authors interpreted the results of their calculations as evidence for a symmetric bond cleavage of H{sub 2} leading directly to two protonated amines in concert with a two-electron reduction of the Ni(II) site to form a Ni(0) diproton state. Proton reduction would involve a reverse symmetric bond formation. We report here an analysis that refutes the interpretation by these authors. We give, for the same model system, the structure of a heterolytic cleavage transition state consistent with the presence of the Ni(II) center acting as a Lewis acid and the pendant amines acting as Lewis bases. We present the associated intrinsic reaction coordinate (IRC) pathway connecting the dihydrogen (?{sup 2}-H{sub 2}) adduct and a hydride–proton state. We report also the transition state and associated IRC for the proton rearrangement from a hydride–proton state to a diproton state. Finally, we complete the characterization of the transition state reported by Vetere et al. through a determination of the corresponding IRC. In summary, H{sub 2} oxidation/proton reduction with this class of catalysts involves a heterolytic bond breaking/formation.

  10. Photoinitiated oxidative addition of CF3I to gold(I) and facile aryl-CF3 reductive elimination.

    PubMed

    Winston, Matthew S; Wolf, William J; Toste, F Dean

    2014-05-28

    Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast Caryl-CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR' (R = Cy, R' = 3,5-F2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R' = 4-F-C6H4, 4-Me-C6H4). When R' = aryl, complexes of the type R3PAu(aryl)(CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (?max = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 °C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor Caryl-I reductive elimination over Caryl-CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu(aryl)(CF3)I results in quantitative formation of Ar-CF3 in less than 1 min at temperatures as low as -10 °C. PMID:24836526

  11. Photoinitiated Oxidative Addition of CF3I to Gold(I) and Facile Aryl-CF3 Reductive Elimination

    PubMed Central

    2015-01-01

    Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast Caryl–CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR? (R = Cy, R? = 3,5-F2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R? = 4-F-C6H4, 4-Me-C6H4). When R? = aryl, complexes of the type R3PAu(aryl)(CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (?max = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 °C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor Caryl–I reductive elimination over Caryl–CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu(aryl)(CF3)I results in quantitative formation of Ar–CF3 in less than 1 min at temperatures as low as ?10 °C. PMID:24836526

  12. ROLE OF MANGANESE REDUCTION/OXIDATION (REDOX) ON FOAMING AND MELT RATE IN HIGH LEVEL WASTE (HLW) MELTERS (U)

    SciTech Connect

    Jantzen, C; Michael Stone, M

    2007-03-30

    High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass and liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn{sub 2}O{sub 3} species to MnO during melter preprocessing. At the lower redox limit of Fe{sup +2}/{summation}Fe {approx} 0.09 about 99% of the Mn{sup +4}/Mn{sup +3} is converted to Mn{sup +2}. Therefore, the lower REDOX limits eliminates melter foaming from deoxygenation.

  13. 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

  14. 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

  15. Accelerated Aging in Schizophrenia Patients: The Potential Role of Oxidative Stress

    PubMed Central

    Okusaga, Olaoluwa O

    2014-01-01

    Several lines of evidence suggest that schizophrenia, a severe mental illness characterized by delusions, hallucinations and thought disorder is associated with accelerated aging. The free radical (oxidative stress) theory of aging assumes that aging occurs as a result of damage to cell constituents and connective tissues by free radicals arising from oxygen-associated reactions. Schizophrenia has been associated with oxidative stress and chronic inflammation, both of which also appear to reciprocally induce each other in a positive feedback manner. The buildup of damaged macromolecules due to increased oxidative stress and failure of protein repair and maintenance systems is an indicator of aging both at the cellular and organismal level. When compared with age-matched healthy controls, schizophrenia patients have higher levels of markers of oxidative cellular damage such as protein carbonyls, products of lipid peroxidation and DNA hydroxylation. Potential confounders such as antipsychotic medication, smoking, socio-economic status and unhealthy lifestyle make it impossible to solely attribute the earlier onset of aging-related changes or oxidative stress to having a diagnosis of schizophrenia. Regardless of whether oxidative stress can be attributed solely to a diagnosis of schizophrenia or whether it is due to other factors associated with schizophrenia, the available evidence is in support of increased oxidative stress-induced cellular damage of macromolecules which may play a role in the phenomenon of accelerated aging presumed to be associated with schizophrenia. PMID:25110609

  16. Electrochemical Oxidation of Ammonia on Ir Anode in Potential Fixed Electrochemical Sensor

    Microsoft Academic Search

    Yi-ping HAN; Peng LUO; Chen-xin CAI; Lei XIE; Tian-hong LU

    2008-01-01

    Ir catalyst possesses a good electrocatalytic activity and selectivity for the oxidation of NH3 and\\/or NH4OH at Ir anode in the potential fixed electrochemical sensor with the neutral solution. Owing to the same electrochemical behavior of NH3 and NH4OH in a NaClO4 solution, NH4OH can be used instead of NH3 for the experimental convenience. It was found that the potential

  17. Reduction of Toxicity and PAH Bioaccumulation Potential During Bioremediation of Petroleum Contaminated Soils

    SciTech Connect

    Huesemann, Michael H.; Hausmann, Tom S.; Fortman, Timothy J.

    2004-03-01

    A set of model soils (e.g., quartz sands, loams, clays, peat, silica gels) was spiked with crude oil, aged for 27 months in the laboratory, and subjected to bench-scale slurry bioremediation treatment for 90 weeks. At various times, slurry samples were removed from the bioreactors, analyzed for polynuclear aromatic hydrocarbons (PAHs), and assayed for toxicity using the solid-phase MicrotoxTM test. In addition, the PAH bioaccumulation potential in tissues of soil dwelling organisms was estimated by exposing semi-permeable membrane devices (SPMDs) for 14 days to initial (t=0) and final (t=90 wks) slurry samples. In most cases, soil toxicity (EC50) was reduced 5- to 10 fold during the first 20 weeks of bioremediation treatment but it rarely reached the EC50 value of the respective clean reference soils, indicating that some residual toxicity still remained after 20 weeks of bioremediation. The reduction of soil toxicity most closely correlated with the biodegradation of the sum of 4, 5, and 6 ring PAHs. A comparison of PAH concentrations in SPMDs exposed to initial and final slurry samples revealed that the potential of PAH accumulation in exposed animal tissues was reduced 50 to 300 fold as a result of slurry biotreatment. While in most soils the bioavailable PAH fraction was preferentially removed by the microorganisms, several high molecular weight PAHs that had reached an apparent concentration asymptote after 90 weeks of treatment were still bioavailable to a significant extent in several soils since they were readily taken up by the SPMDs. In summary, it can be concluded that bioremediation significantly reduces both toxicity and PAH bioaccumulation potential. However, the remaining undegraded contaminants are likely to pose some residual risk to environmental receptors since they still exhibit toxicity relative to uncontaminated background soils and are bioavailable to animal tissues.

  18. The Demand Reduction Potential of Smart Appliances in U.S. Homes

    SciTech Connect

    Makhmalbaf, Atefe; Srivastava, Viraj; Parker, Graham B.

    2013-08-14

    The widespread deployment of demand respond (DR) enabled home appliances is expected to have significant reduction in the demand of electricity during peak hours. The work documented in this paper focuses on estimating the energy shift resulting from the installation of DR enabled smart appliances in the U.S. This estimation is based on analyzing the market for smart appliances and calculating the total energy demand that can potentially be shifted by DR control in appliances. Appliance operation is examined by considering their sub components individually to identify their energy consumptions and savings resulting from interrupting and shifting their load, e.g., by delaying the refrigerator defrost cycle. In addition to major residential appliances, residential pool pumps are also included in this study given their energy consumption profiles that make them favorable for DR applications. In the market analysis study documented in this paper, the U.S. Energy Information Administration's (EIA) Residential Energy Consumption Survey (RECS) and National Association of Home Builders (NAHB) databases are used to examine the expected life of an appliance, the number of appliances installed in homes constructed in 10 year intervals after 1940 and home owner income. Conclusions about the effectiveness of the smart appliances in reducing electrical demand have been drawn and a ranking of appliances in terms of their contribution to load shift is presented. E.g., it was concluded that DR enabled water heaters result in the maximum load shift; whereas, dishwashers have the highest user elasticity and hence the highest potential for load shifting through DR. This work is part of a larger effort to bring novel home energy management concepts and technologies to reduce energy consumption, reduce peak electricity demand, integrate renewables and storage technology, and change homeowner behavior to manage and consume less energy and potentially save consumer energy costs.

  19. Metabolic-flux analysis of hybridoma cells under oxidative and reductive stress using mass balances

    Microsoft Academic Search

    Hendrik P. J. Bonarius; José H. M. Houtman; Georg Schmid; Cornelis D. de Gooijer; Johannes Tramper

    2000-01-01

    Hybridoma cells were grown at steady state under both reductiveand oxidative stress and the intracellular fluxes weredetermined by mass-balancing techniques. By decreasing the dissolved oxygen pressure (pO2) in the bioreactor, the reduced formof nicotinamide adenine nucleotide (NADH) was enhanced relativeto the oxidized form (NAD+). Oxidative stress, as a resultof which the NAP(P)+\\/NAD(P)H-ratio increases, was generatedby both the enhancement of the

  20. Investigating the function of [2Fe–2S] cluster N1a, the off-pathway cluster in complex I, by manipulating its reduction potential

    PubMed Central

    Birrell, James A.; Morina, Klaudia; Bridges, Hannah R.; Friedrich, Thorsten; Hirst, Judy

    2013-01-01

    NADH:quinone oxidoreductase (complex I) couples NADH oxidation and quinone reduction to proton translocation across an energy-transducing membrane. All complexes I contain a flavin to oxidize NADH, seven iron–sulfur clusters to transfer electrons from the flavin to quinone and an eighth cluster (N1a) on the opposite side of the flavin. The role of cluster N1a is unknown, but Escherichia coli complex I has an unusually high-potential cluster N1a and its reduced flavin produces H2O2, not superoxide, suggesting that cluster N1a may affect reactive oxygen species production. In the present study, we combine protein film voltammetry with mutagenesis in overproduced N1a-binding subunits to identify two residues that switch N1a between its high- (E. coli, valine and asparagine) and low- (Bos taurus and Yarrowia lipolytica, proline and methionine) potential forms. The mutations were incorporated into E. coli complex I: cluster N1a could no longer be reduced by NADH, but H2O2 and superoxide production were unaffected. The reverse mutations (that increase the potential by ~0.16 V) were incorporated into Y. lipolytica complex I, but N1a was still not reduced by NADH. We conclude that cluster N1a does not affect reactive oxygen species production by the complex I flavin; it is probably required for enzyme assembly or stability. PMID:23980528

  1. 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.

  2. 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.

  3. A comprehensive skeletal mechanism for the oxidation of n-heptane generated by chemistry-guided reduction

    SciTech Connect

    Zeuch, Thomas [Institut fuer Physikalische Chemie, Tammannstrasse 6, 37077 Goettingen (Germany); Moreac, Gladys [Renault, 1, avenue du Golf, 78288 Guyancourt cedex (France); Ahmed, Syed Sayeed; Mauss, Fabian [Lehrstuhl fuer Thermodynamik und Thermische Verfahrenstechnik, Sielower Strasse 12, 03044 Cottbus (Germany)

    2008-12-15

    Applied to the primary reference fuel n-heptane, we present the chemistry-guided reduction (CGR) formalism for generating kinetic hydrocarbon oxidation models. The approach is based on chemical lumping and species removal with the necessity analysis method, a combined reaction flow and sensitivity analysis. Independent of the fuel size, the CGR formalism generates very compact submodels for the alkane low-temperature oxidation and provides a general concept for the development of compact oxidation models for large model fuel components such as n-decane and n-tetradecane. A defined sequence of simplification steps, consisting of the compilation of a compact detailed chemical model, the application of linear chemical lumping, and finally species removal based on species necessity values, allows a significantly increased degree of reduction compared to the simple application of the necessity analysis, previously published species, or reaction removal methods. The skeletal model derived by this procedure consists of 110 species and 1170 forward and backward reactions and is validated against the full range of combustion conditions including low and high temperatures, fuel-lean and fuel-rich mixtures, pressures between 1 and 40 bar, and local (species concentration profiles in flames, plug flow and jet-stirred reactors, and reaction sensitivity coefficients) and global parameters (ignition delay times in shock tube experiments, ignition timing in a HCCI engine, and flame speeds). The species removal is based on calculations using a minimum number of parameter configurations, but complemented by a very broad parameter variation in the process of compiling the kinetic input data. We further demonstrate that the inclusion of sensitivity coefficients in the validation process allows efficient control of the reduction process. Additionally, a compact high-temperature n-heptane oxidation model of 47 species and 468 reactions was generated by the application of necessity analysis to the skeletal mechanism. (author)

  4. 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

  5. SCR Atmosphere Induced Reduction of Oxidized Mercury over CuO-CeO2/TiO2 Catalyst.

    PubMed

    Li, Hailong; Wu, Shaokang; Wu, Chang-Yu; Wang, Jun; Li, Liqing; Shih, Kaimin

    2015-06-16

    CuO-CeO2/TiO2 (CuCeTi) catalyst synthesized by a sol-gel method was employed to investigate mercury conversion under a selective catalytic reduction (SCR) atmosphere (NO, NH3 plus O2). Neither NO nor NH3 individually exhibited an inhibitive effect on elemental mercury (Hg(0)) conversion in the presence of O2. However, Hg(0) conversion over the CuCeTi catalyst was greatly inhibited under SCR atmosphere. Systematic experiments were designed to investigate the inconsistency and explore the in-depth mechanisms. The results show that the copresence of NO and NH3 induced reduction of oxidized mercury (Hg(2+), HgO in this study), which offset the effect of catalytic Hg(0) oxidation, and hence resulted in deactivation of Hg(0) conversion. High NO and NH3 concentrations with a NO/NH3 ratio of 1.0 facilitated Hg(2+) reduction and therefore lowered Hg(0) conversion. Hg(2+) reduction over the CuCeTi catalyst was proposed to follow two possible mechanisms: (1) direct reaction, in which NO and NH3 react directly with HgO to form N2 and Hg(0); (2) indirect reaction, in which the SCR reaction consumed active surface oxygen on the CuCeTi catalyst, and reduced species on the CuCeTi catalyst surface such as Cu2O and Ce2O3 robbed oxygen from adjacent HgO. Different from the conventionally considered mechanisms, that is, competitive adsorption responsible for deactivation of Hg(0) conversion, this study reveals that oxidized mercury can transform into Hg(0) under SCR atmosphere. Such knowledge is of fundamental importance in developing efficient and economical mercury control technologies for coal-fired power plants. PMID:25961487

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

    PubMed

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

    2015-01-01

    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. PMID:25994393

  7. Decomposition and reduction of NO on transition metal surfaces: bond order conservation Morse potential analysis

    NASA Astrophysics Data System (ADS)

    Shustorovich, Evgeny; Bell, Alexis T.

    1993-05-01

    Periodic trends in the decomposition of NO and its reduction to N 2 and NH 3 by CO and H 2 on transition metal surfaces have been analyzed theoretically using the bond order conservation Morse potential (BOCMP) method. The analysis is based on calculations of the energetics, the reaction enthalpies ?H and activation barriers ?H ?, of elementary steps thought to comprise the mechanisms of the NO transformations. As the periodic series, the close-packed surfaces Pt(111), Rh(111), Ru(001), and Re(001) were chosen. The calculated heats of chemisorption Q of NH 3, NH 2, NH, NO, H 2O and OH are in good agreement with experiment. The activation barriers for dissociation of NO from a chemisorbed state, ?E NOs? were found to decrease in the order Pt > Rh > Ru > Re. For reasonable values of QN and QO, in the zero-coverage extreme these activation barriers were calculated to be much smaller than the relevant heats of chemisorption QNO, so that dissociation of No upon heating is projected for all the surfaces studied with the possible exception of Pt(111). The presence of adsorbed N S and O S atoms may dramatically increase the values of ?E NOS?, for example, from 7-9 to 24-27 kcal/mol for Rh(100) and Rh(100)c(2 × 2)O,N, respectively. This sensitiv the values of ?E NOs? to NO S coverage may explain the diversity of experimental results obtained for different coverages (exposu and temperatures even for the same single crystal face. The anisotropy of the values of QX(X = NO, N, O) for different surfaces and possible reconstructions of these surfaces also contribute to the balance between dissociation and desorption of NO. Of the two channels for recombinative desorption of N 2, 2N S? N 2,g and N S + NO S? N 2,g + O S, the latter has the smaller activati barrier. Because the N 2 formation barriers rapidly increase in the order Pt ˜ Rh ? Ru ? Re, Rh or Rh-Pt surfaces are projected to be the most efficient catalysts for NO reduction by CO (to N 2 and CO 2). Similarly, Pt surfaces are projected to be the most efficient catalysts for NO reduction by H 2 (to NH 3 and H 2O). The general mechanistic picture emerging from the BOCMP analysis concurs with experimental data. Some apparent inconsistencies, particularly concerning the dissociation of NO, are discussed and some model conclusions to be verified by future experiments are noted.

  8. Reduction of PCDDs/PCDFs in MSWI fly ash using microwave peroxide oxidation in H2SO4/HNO3 solution.

    PubMed

    Chang, Yu-Min; Dai, Wen-Chien; Tsai, Kao-Shen; Chen, Shiao-Shing; Chen, Jyh-Herng; Kao, Jimmy C M

    2013-05-01

    Microwave peroxide oxidation (MPO) is an energy-efficient and low GHG emission technology to destroy the hazardous organic compounds in solid waste. The objective of this paper is to explore the reduction feasibility of PCDDs/Fs in MSWI fly ash using the MPO in H2SO4/HNO3 solution. Nearly all PCDDs/Fs, 99% in the original fly ash, can be reduced in 120min at the temperature of 150°C using the MPO treatment. It was also found that a change occurred in the content distribution profiles of 17 major PCDD/F congeners before and after MPO treatment. This provides the potential to reduce the actual PCDDs/Fs content more than I-TEQ contents of PCDDs/Fs. The percentile distribution profile has a tendency of higher chlorinated PCDDs/Fs moving to the lower ones. It concludes that a significant reduction efficiency of I-TEQ toxicity was achieved and showed sufficient reduction of toxic level to lower than 1.0ngI-TEQ(gdw)(-1). The treatment temperature would be a critical factor facilitating the dissolution because higher temperature leads more inorganic salt (parts of fly ash) dissolution. Some problems caused by the MPO method are also delineated in this paper. PMID:23453433

  9. A new form of cerebellar long-term potentiation is postsynaptic and depends on nitric oxide but

    E-print Network

    Tsien, Roger Y.

    A new form of cerebellar long-term potentiation is postsynaptic and depends on nitric oxide and requires cAMP but not nitric oxide. It is a poor candidate to reverse LTD because it is presynaptically , and depends on nitric oxide but not cAMP or cGMP, making it a plausible anti-Hebbian counterpart to Hebbian

  10. Classification of metal-oxide bonded interactions based on local potential-and kinetic-energy densities

    E-print Network

    Crawford, T. Daniel

    Classification of metal-oxide bonded interactions based on local potential- and kinetic number of oxide molecules and earth materials, together with the constraints imposed by the values of 2 the same classification for the oxides. This is true despite the different trends that hold between

  11. Influence of fibre surface oxidation–reduction followed by silsesquioxane coating treatment on interfacial mechanical properties of carbon fibre\\/polyarylacetylene composites

    Microsoft Academic Search

    Xuezhong Zhang; Yudong Huang; Tianyu Wang; Li Liu

    2007-01-01

    Carbon fibre was treated with oxidation–reduction followed by silsesquioxane coating method to improve the interfacial properties of carbon fibre\\/polyarylacetylene (CF\\/PAA) composites. The treatment method was divided into three phases, i.e., oxidation with oxygen plasma, reduction with LiAlH4, and coating treatment with vinyl silsesquioxane (VMS–SSO). The fibre surface composition and functional group were analyzed using X-ray photoelectron spectroscopy (XPS). The polar

  12. Reaction mechanism reduction and optimisation for modelling aviation fuel oxidation using standard and hybrid genetic algorithms

    Microsoft Academic Search

    Lionel Elliott; Derek B. Ingham; Adrian G. Kyne; Nicolae S. Mera; Mohamed Pourkashanian; Sean Whittaker

    2006-01-01

    This study describes the development of a new binary encoded genetic algorithm for the combinatorial problem of determining a subset of species and their associated reactions that best represent the full starting point reaction mechanism in modelling aviation fuel oxidation. The genetic algorithm has a dual objective in finding a reduced mechanism that best represents aviation fuel oxidation in both

  13. Original Contribution Iron chelators can protect against oxidative stress through ferryl heme reduction

    Microsoft Academic Search

    Brandon J. Reeder; Robert C. Hider; Michael T. Wilson

    Iron chelators such as desferrioxamine have been shown to ameliorate oxidative damage in vivo. The mechanism of this therapeutic action under non-iron-overload conditions is, however, complex, as desferrioxamine has properties that can impact on oxidative damage independent of its capacity to act as an iron chelator. Desferrioxamine can act as a reducing agent to remove cytotoxic ferryl myoglobin and hemoglobin

  14. Reduction of Stratospheric Ozone by Nitrogen Oxide Catalysts from Supersonic Transport Exhaust

    Microsoft Academic Search

    Harold Johnston

    1971-01-01

    Although a great deal of attention has been given to the role of water vapor from supersonic transport (SST) exhaust in the stratosphere, oxides of nitrogen from SST exhaust pose a much greater threat to the ozone shield than does an increase in water. The projected increase in stratospheric oxides of nitrogen could reduce the ozone shield by about a

  15. 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

    ); (c) V. M. Bzhezovskii, E. G. Kapustin. Russ. J. Gen. Chem. 73, 54 (2003). 23. H. Fujihara, Y. Higuchi, H. Mima, N. Furukawa. Chem. Lett. 619 (1994). 24. H. Fujihara, R. Akaishi, N. Furukawa. Chem. Lett. 549 (1990). 25. For oxidation potentials...-Centered Reactive Intermediates in Chemistry and Biology, C. Chatgilialoglu, K.-D. Asmus (Eds.), NATO ASI series 197, pp. 213–226, Plenum Press, New York (1990); (b) R. S. Glass. Rev. Heteroatom. Chem. 15, 1 (1996). © 2010, IUPAC Pure Appl. Chem., Vol. 82, No. 3, pp...

  16. Bacterial enzymes for dissimilatory sulfate reduction in a marine microbial mat (Black Sea) mediating anaerobic oxidation of methane.

    PubMed

    Basen, Mirko; Krüger, Martin; Milucka, Jana; Kuever, Jan; Kahnt, Jörg; Grundmann, Olav; Meyerdierks, Anke; Widdel, Friedrich; Shima, Seigo

    2011-05-01

    Anaerobic oxidation of methane (AOM) with sulfate is catalysed by microbial consortia of archaea and bacteria affiliating with methanogens and sulfate-reducing Deltaproteobacteria respectively. There is evidence that methane oxidation is catalysed by enzymes related to those in methanogenesis, but the enzymes for sulfate reduction coupled to AOM have not been examined. We collected microbial mats with high AOM activity from a methane seep in the Black Sea. The mats consisted mainly of archaea of the ANME-2 group and bacteria of the Desulfosarcina-Desulfococcus group. Cell-free mat extract contained activities of enzymes involved in sulfate reduction to sulfide: ATP sulfurylase (adenylyl : sulfate transferase; Sat), APS reductase (Apr) and dissimilatory sulfite reductase (Dsr). We partially purified the enzymes by anion-exchange chromatography. The amounts obtained indicated that the enzymes are abundant in the mat, with Sat accounting for 2% of the soluble mat protein. N-terminal amino acid sequences of purified proteins suggested similarities to the corresponding enzymes of known species of sulfate-reducing bacteria. The deduced amino acid sequence of PCR-amplified genes of the Apr subunits is similar to that of Apr of the Desulfosarcina/Desulfococcus group. These results indicate that the major enzymes involved in sulfate reduction in the Back Sea microbial mats are of bacterial origin, most likely originating from the bacterial partner in the consortium. PMID:21392199

  17. Neutralization potential determination of siderite (FeCO{sub 3}) using selected oxidants

    SciTech Connect

    Haney, E.B.; Haney, R.L.; Hossner, L.R.; White, G.N. [Texas A& amp; M University, College Station, TX (United States). Dept. of Soil & Crop Science

    2006-05-15

    Siderite (FeCO{sub 3}) is commonly found in coal overburden and, when present, can cause interference in the determination of neutralization potential (NP). Under acidic testing conditions, FeCO{sub 3} reacts to neutralize acid, which contributes to the NP. However, continued weathering of FeCO{sub 3} (oxidation of Fe{sup 2+} and hydrolysis of Fe{sup 3+}) produces a neutral to slightly acidic solution. The effects of hydrogen peroxide (H{sub 2}O{sub 2}), potassium permanganate (KMnO{sub 4}), and O{sub 2} on the laboratory measurement of NP of siderite samples taken from overburden were examined. All oxidation treatments lowered the NP values of the siderite samples as compared with the standard USEPA method. However, oxidation with H{sub 2}O{sub 2} produced variable results depending on the amount of H{sub 2}O{sub 2} added. Neutralization potential values obtained after oxidation treatments were highly correlated with Mn concentration. Reaction products (i.e., 2-line ferrihydrite) of siderite samples with H{sub 2}O{sub 2} and KMnO{sub 4} were not representative of natural siderite weathering. Oxidation with O{sub 2} produced the lowest NP values for siderite samples. The reaction products produced by oxidation with O{sub 2} most closely represent those intermediate products formed when siderite is exposed to atmospheric weathering conditions. Oxidation with O{sub 2} also proved to be the most reproducible method for accurately assessing NP when siderite is present in overburden samples.

  18. Estimation of Injected Carbon Longevity and Re-oxidation Times at Enhanced Reductive Bioremediation Sites

    NASA Astrophysics Data System (ADS)

    Tillotson, J.; Borden, R. C.

    2014-12-01

    Addition of an organic substrate to provide an electron donor and carbon source can be very effective at stimulating enhanced reductive bioremediation (ERB) of chlorinated solvents, energetics, and other groundwater contaminants. However, the quantity of electron donor added is usually based on an individual's or company's "rule of thumb" rather than considering site-specific conditions such as groundwater velocity, carbon source, and upgradient electron acceptor concentrations, potentially leading to unnecessarily large amounts of carbon injected. Mass balance estimates indicate that over 99% of electrons donated go to electron acceptors other than the primary contaminants. Thus, injecting excessive amounts of organic carbon can lead to a persistent reducing zone, releasing elevated levels of dissolved manganese, iron, methane, and sometimes arsenic. Monitoring data on carbon injections and electron acceptors were collected from 33 ERB sites. Two approaches were then used to evaluate carbon longevity and the time required to return to near-oxic conditions at an ERB site. The first method employed a simple mass balance approach, using such input parameters as groundwater velocity, upgradient electron acceptors, and amount of carbon injected. In the second approach, a combined flow, transport and geochemical model was developed using PHT3D to estimate the impact of ERB on secondary water quality impacts (SWQIs; e.g., methane production, iron mobilization and transport, etc.) The model was originally developed for use in estimating SWQIs released from petroleum sites, but has since been modified for use at ERB sites. The ERB site to be studied is a perchlorate release site in Elkton, Maryland where 840 lbs of an emulsified vegetable oil was injected. The results from the simple mass balance approach and PHT3D model will be compared and used to identify conditions where the simplified approach may be appropriate.

  19. Interaction of nitric oxide with non-haem iron sites of Escherichia coli bacterioferritin: reduction of nitric oxide to nitrous oxide and oxidation of iron(II) to iron(III).

    PubMed Central

    Le Brun, N E; Andrews, S C; Moore, G R; Thomson, A J

    1997-01-01

    The bacterioferritin (BFR) of Escherichia coli consists of 24 identical subunits, each containing a dinuclear metal-binding site consisting of two histidines and four carboxylic acid residues. Earlier studies showed that the characterization of iron binding to BFR could be aided by EPR analysis of iron-nitrosyl species resulting from the addition of NO to the protein [Le Brun, Cheesman, Andrews, Harrison, Guest, Moore and Thomson (1993) FEBS Lett. 323, 261-266]. We now report data from gas chromatographic head space analysis combined with EPR spectroscopy to show that NO is not an inert probe: iron(II)-BFR catalyses the reduction of NO to N2O, resulting in oxidation of iron(II) at the dinuclear centre and the subsequent detection of mononuclear iron(III). In the presence of excess reductant (sodium ascorbate), iron(II)-BFR also catalyses the reduction of NO to N2O, giving rise to three mononuclear iron-nitrosyl species which are detectable by EPR. One of these, a dinitrosyl-iron complex of S = 1/2, present at a maximum of one per subunit, is shown by EPR studies of site-directed variants of BFR not to be located at the dinuclear centre. This is consistent with a proposal that the diferric form of the centre is unstable and breaks down to form mononuclear iron species. PMID:9337865

  20. Sterically stabilized liposomes. Reduction in electrophoretic mobility but not electrostatic surface potential.

    PubMed Central

    Woodle, M C; Collins, L R; Sponsler, E; Kossovsky, N; Papahadjopoulos, D; Martin, F J

    1992-01-01

    The electrophoretic mobility of liposomes containing a negatively charged derivative of phosphatidylethanolamine with a large headgroup composed of the hydrophilic polymer polyethylene glycol (PEG-PE) was determined by Doppler electrophoretic light scattering. The results show that this method is improved by the use of measurements at multiple angles to eliminate artifacts and that very small mobilities can be measured. The electrophoretic mobility of liposomes with 5 to 10 mol% PEG-PE is approximately -0.5 mu ms-1/Vcm-1 regardless of PEG-PE content compared with approximately -2 mu ms-1/Vcm-1 for similar liposomes but containing 7.5% phosphatidylglycerol (PG) instead of PEG-PE. Measurements of surface potential by distribution of an anionic fluorescent probe show that the PEG-PE imparts a negative charge identical to that by PG, consistent with the expectation of similar locations of the ionized phosphate responsible for the charge. The reduced mobility imparted by the surface bound PEG is attributed to a mechanism similar to that described for colloidal steric stabilization: hydrodynamic drag moves the hydrodynamic plane of shear, or the hydrodynamic radius, away from the charge-bearing plane, that of the phosphate moities. An extended length of approximately 50 A for the 2,000 molecular weight PEG is estimated from the reduction in electrophoretic mobility. PMID:1581503