Science.gov

Sample records for fuel reactivity formation

  1. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-11-25

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  2. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-01-21

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  3. Engine combustion control via fuel reactivity stratification

    DOEpatents

    Reitz, Rolf Deneys; Hanson, Reed M.; Splitter, Derek A.; Kokjohn, Sage L.

    2016-06-28

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  4. Engine combustion control via fuel reactivity stratification

    DOEpatents

    Reitz, Rolf Deneys; Hanson, Reed M; Splitter, Derek A; Kokjohn, Sage L

    2013-12-31

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choose the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  5. Engine combustion control via fuel reactivity stratification

    DOEpatents

    Reitz, Rolf Deneys; Hanson, Reed M.; Splitter, Derek A.; Kokjohn, Sage L.

    2015-07-14

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  6. Heating subsurface formations by oxidizing fuel on a fuel carrier

    DOEpatents

    Costello, Michael; Vinegar, Harold J.

    2012-10-02

    A method of heating a portion of a subsurface formation includes drawing fuel on a fuel carrier through an opening formed in the formation. Oxidant is supplied to the fuel at one or more locations in the opening. The fuel is combusted with the oxidant to provide heat to the formation.

  7. Biodiesel Fuel Property Effects on Particulate Matter Reactivity

    SciTech Connect

    Williams, A.; Black, S.; McCormick, R. L.

    2010-06-01

    Controlling diesel particulate emissions to meet the 2007 U.S. standard requires the use of a diesel particulate filter (DPF). The reactivity of soot, or the carbon fraction of particulate matter, in the DPF and the kinetics of soot oxidation are important in achieving better control of aftertreatment devices. Studies showed that biodiesel in the fuel can increase soot reactivity. This study therefore investigated which biodiesel fuel properties impact reactivity. Three fuel properties of interest included fuel oxygen content and functionality, fuel aromatic content, and the presence of alkali metals. To determine fuel effects on soot reactivity, the performance of a catalyzed DPF was measured with different test fuels through engine testing and thermo-gravimetric analysis. Results showed no dependence on the aromatic content or the presence of alkali metals in the fuel. The presence and form of fuel oxygen was the dominant contributor to faster DPF regeneration times and soot reactivity.

  8. Assessment of reactivity transient experiments with high burnup fuel

    SciTech Connect

    Ozer, O.; Yang, R.L.; Rashid, Y.R.; Montgomery, R.O.

    1996-03-01

    A few recent experiments aimed at determining the response of high-burnup LWR fuel during a reactivity initiated accident (RIA) have raised concerns that existing failure criteria may be inappropriate for such fuel. In particular, three experiments (SPERT CDC-859, NSRR HBO-1 and CABRI REP Na-1) appear to have resulted in fuel failures at only a fraction of the anticipated enthalpy levels. In evaluating the results of such RIA simulation experiments, however, it is necessary that the following two key considerations be taken into account: (1) Are the experiments representative of conditions that LWR fuel would experience during an in-reactor RIA event? (2) Is the fuel that is being utilized in the tests representative of the present (or anticipated) population of LWR fuel? Conducting experiments under conditions that can not occur in-reactor can trigger response modes that could not take place during in-reactor operation. Similarly, using unrepresentative fuel samples for the tests will produce failure information that is of limited relevance to commercial LWR fuel. This is particularly important for high-burnup fuel since the manner under which the test samples are base-irradiated prior to the test will impact the mechanical properties of the cladding and will therefore affect the RIA response. A good example of this effect can be seen in the results of the SPERT CDC-859 test and in the NSRR JM-4 and JM-5 tests. The conditions under which the fuel used for these tests was fabricated and/or base-irradiated prior to the RIA pulse resulted in the formation of multiple cladding defects in the form of hydride blisters. When this fuel was subjected to the RIA power pulse, it failed by developing multiple cracks that were closely correlated with the locations of the pre-existing hydride blisters. In the case of the JM tests, many of the cracks formed within the blisters themselves and did not propagate beyond the heavily hydrided regions.

  9. Formate Formation and Formate Conversion in Biological Fuels Production

    PubMed Central

    Crable, Bryan R.; Plugge, Caroline M.; McInerney, Michael J.; Stams, Alfons J. M.

    2011-01-01

    Biomethanation is a mature technology for fuel production. Fourth generation biofuels research will focus on sequestering CO2 and providing carbon-neutral or carbon-negative strategies to cope with dwindling fossil fuel supplies and environmental impact. Formate is an important intermediate in the methanogenic breakdown of complex organic material and serves as an important precursor for biological fuels production in the form of methane, hydrogen, and potentially methanol. Formate is produced by either CoA-dependent cleavage of pyruvate or enzymatic reduction of CO2 in an NADH- or ferredoxin-dependent manner. Formate is consumed through oxidation to CO2 and H2 or can be further reduced via the Wood-Ljungdahl pathway for carbon fixation or industrially for the production of methanol. Here, we review the enzymes involved in the interconversion of formate and discuss potential applications for biofuels production. PMID:21687599

  10. Formation and Reactivity of Biogenic Iron Microminerals

    SciTech Connect

    Beveridge, Terrance J.; Glasauer, Susan; Korenevsky, Anton; Ferris, F. Grant

    2000-08-08

    The overall purpose of the project is to explore and quantify the processes that control the formation and reactivity of biogenic iron microminerals and their impact on the solubility of metal contaminants. The research addresses how surface components of bacterial cells, extracellular organic material, and the aqueous geochemistry of the DIRB microenvironment impacts the mineralogy, chemical state and micromorphology of reduced iron phases.

  11. Reactive spreading: Adsorption, ridging and compound formation

    SciTech Connect

    Saiz, E.; Cannon, R.M.; Tomsia, A.P.

    2000-09-11

    Reactive spreading, in which a chemically active element is added to promote wetting of noble metals on nonmetallic materials, is evaluated. Theories for the energetics and kinetics of the necessary steps involved in spreading are outlined and compared to the steps in compound formation that typically accompany reactive wetting. These include: fluid flow, active metal adsorption, including nonequilibrium effects, and triple line ridging. All of these can be faster than compound nucleation under certain conditions. Analysis and assessment of recently reported experiments on metal/ceramic systems lead to a focus on those conditions under which spreading proceeds ahead of the actual formation of a new phase at the interface. This scenario may be more typical than believed, and perhaps the most effective situation leading to enhanced spreading. A rationale for the pervasive variability and hysteresis observed during high temperature wetting also emerges.

  12. Formation and Reactivity of Biogenic Iron Microminerals

    SciTech Connect

    Beveridge, Terrance J.; Ferris, F. Grant

    1999-06-01

    The overall purpose of the project is to explore and quantify the processes that control the formation and reactivity of biogenic iron microminerals, and the impact of these processes on the solubility of metal contaminants, e.g., uranium, chromium and nickel. The research addresses how surface components of bacterial cells, extracellular organic material, and the aqueous geochemistry of the DIRB microenvironment impacts the mineralogy, chemical state and micromorphology of reduced iron phases.

  13. Reactive flash volatilization of fluid fuels

    DOEpatents

    Schmidt, Lanny D.; Dauenhauer, Paul J.; Dreyer, Bradon J.; Salge, James R.

    2013-01-08

    The invention provides methods for the production of synthesis gas. More particularly, various embodiments of the invention relate to systems and methods for volatilizing fluid fuel to produce synthesis gas by using a metal catalyst on a solid support matrix.

  14. Critical role of water content in the formation and reactivity of uranium, neptunium, and plutonium iodates under hydrothermal conditions: implications for the oxidative dissolution of spent nuclear fuel.

    PubMed

    Bray, Travis H; Ling, Jie; Choi, Eun Sang; Brooks, James S; Beitz, James V; Sykora, Richard E; Haire, Richard G; Stanbury, David M; Albrecht-Schmitt, Thomas E

    2007-04-30

    The reactions of 237NpO2 with excess iodate under acidic hydrothermal conditions result in the isolation of the neptunium(IV), neptunium(V), and neptunium(VI) iodates, Np(IO3)4, Np(IO3)4.nH2O.nHIO3, NpO2(IO3), NpO2(IO3)2(H2O), and NpO2(IO3)2.H2O, depending on both the pH and the amount of water present in the reactions. Reactions with less water and lower pH favor reduced products. Although the initial redox processes involved in the reactions between 237NpO2 or 242PuO2 and iodate are similar, the low solubility of Pu(IO3)4 dominates product formation in plutonium iodate reactions to a much greater extent than does Np(IO3)4 in the neptunium iodate system. UO2 reacts with iodate under these conditions to yield uranium(VI) iodates solely. The isotypic structures of the actinide(IV) iodates, An(IO3)4 (An=Np, Pu), are reported and consist of one-dimensional chains of dodecahedral An(IV) cations bridged by iodate anions. The structure of Np(IO3)4.nH2O.nHIO3 is constructed from NpO9 tricapped-trigonal prisms that are bridged by iodate into a polar three-dimensional framework structure. Second-harmonic-generation measurements on a polycrystalline sample of the Th analogue of Np(IO3)4.nH2O.nHIO3 reveal a response of approximately 12x that of alpha-SiO2. Single-crystal magnetic susceptibility measurements of Np(IO3)4 show magnetically isolated Np(IV) ions.

  15. Deposit formation in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Roback, R.; Szetela, E. J.; Spadaccini, L. J.

    1981-01-01

    An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811 K. Results indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800 K, with peak deposit formation occurring near 700 K. No improvements were obtained when deoxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. Results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, lating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

  16. Direct formate fuel cells: A review

    NASA Astrophysics Data System (ADS)

    An, L.; Chen, R.

    2016-07-01

    Direct formate fuel cells (DFFC), which convert the chemical energy stored in formate directly into electricity, are recently attracting more attention, primarily because of the use of the carbon-neutral fuel and the low-cost electrocatalytic and membrane materials. As an emerging energy technology, the DFFC has made a rapid progress in recent years (currently, the state-of-the-art power density is 591 mW cm-2 at 60 °C). This article provides a review of past research on the development of this type of fuel cell, including the working principle, mechanisms and materials of the electrocatalytic oxidation of formate, singe-cell designs and performance, as well as innovative system designs. In addition, future perspectives with regard to the development of this fuel cell system are also highlighted.

  17. Engine combustion control at low loads via fuel reactivity stratification

    DOEpatents

    Reitz, Rolf Deneys; Hanson, Reed M; Splitter, Derek A; Kokjohn, Sage L

    2014-10-07

    A compression ignition (diesel) engine uses two or more fuel charges during a combustion cycle, with the fuel charges having two or more reactivities (e.g., different cetane numbers), in order to control the timing and duration of combustion. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot). At low load and no load (idling) conditions, the aforementioned results are attained by restricting airflow to the combustion chamber during the intake stroke (as by throttling the incoming air at or prior to the combustion chamber's intake port) so that the cylinder air pressure is below ambient pressure at the start of the compression stroke.

  18. Fuels for fuel cells: Fuel and catalyst effects on carbon formation

    SciTech Connect

    Borup, R. L.; Inbody, M. A.; Perry, W. L.; Parkinson, W. J. ,

    2002-01-01

    The goal of this research is to explore the effects of fuels, fuel constituents, additives and impurities on the performance of on-board hydrogen generation devices and consequently on the overall performance of fuel cell systems using reformed hydrocarbon fuels. Different fuels and components have been tested in automotive scale, adiabatic autothermal reactors to observe their relative reforming characteristics with various operating conditions. Carbon formation has been modeled and was experimentally monitored in situ during operation by laser measurements of the effluent reformate. Ammonia formation was monitored, and conditions varied to observe under what conditions N H 3 is made.

  19. Formation and Detoxification of Reactive Oxygen Species

    ERIC Educational Resources Information Center

    Kuciel, Radoslawa; Mazurkiewicz, Aleksandra

    2004-01-01

    A model of reactive oxygen species metabolism is proposed as a laboratory exercise for students. The superoxide ion in this model is generated during the reaction of oxidation of xanthine, catalyzed by xanthine oxidase. The effect of catalase, superoxide dismutase, and allopurinol on superoxide ion generation and removal in this system is also…

  20. Formation and Reactivity of Biogenic Iron Minerals

    SciTech Connect

    Ferris, F. Grant

    2003-06-01

    In the current study we aimed to determine how the cell surface polymers, such as lipopolysaccharide (LPS) and capsular material, of a number of strains of Shewanella influenced surface proton binding behavior. An investigation of this kind is pertinent as surface proton binding site reactivity may influence a number of important eco-physiological factors. For example, proton binding sites may sequester Fe2+, as well as other metals like Ni2+, and thus inhibit the supply and metabolic reduction of Fe3+.(Parmar et al. 2001) Further understanding the cell surface reactivity of Shewanella is also important as this may influence the ability of the microorganism to adhere and interact with metal oxides and hydroxides. This study combined acid-base titration analyses to determine proton binding behavior with SDS-PAGE analysis of LPS.

  1. Mitochondrial formation of reactive oxygen species

    PubMed Central

    Turrens, Julio F

    2003-01-01

    The reduction of oxygen to water proceeds via one electron at a time. In the mitochondrial respiratory chain, Complex IV (cytochrome oxidase) retains all partially reduced intermediates until full reduction is achieved. Other redox centres in the electron transport chain, however, may leak electrons to oxygen, partially reducing this molecule to superoxide anion (O2−•). Even though O2−• is not a strong oxidant, it is a precursor of most other reactive oxygen species, and it also becomes involved in the propagation of oxidative chain reactions. Despite the presence of various antioxidant defences, the mitochondrion appears to be the main intracellular source of these oxidants. This review describes the main mitochondrial sources of reactive species and the antioxidant defences that evolved to prevent oxidative damage in all the mitochondrial compartments. We also discuss various physiological and pathological scenarios resulting from an increased steady state concentration of mitochondrial oxidants. PMID:14561818

  2. String cavitation formation inside fuel injectors

    NASA Astrophysics Data System (ADS)

    Reid, B. A.; Gavaises, M.; Mitroglou, N.; Hargrave, G. K.; Garner, C. P.; McDavid, R. M.

    2015-12-01

    The formation of vortex or ‘string’ cavitation has been visualised at pressures up to 2000 bar in an automotive-sized optical diesel fuel injector nozzle. The multi-hole nozzle geometry studied allowed observation of the hole-to-hole vortex interaction and, in particular, that of a bridging vortex in the sac region between the holes. Above a threshold Reynolds number, their formation and appearance during a 2 ms injection event was repeatable and independent of upstream pressure and cavitation number. In addition, two different hole layouts and threedimensional flow simulations have been employed to describe how, the relative positions of adjacent holes influenced the formation and hole-to-hole interaction of the observed string cavitation vortices, with good agreement between the experimental and simulation results being achieved.

  3. Formation and Reactivity of Biogenic Iron Minerals

    SciTech Connect

    Ferris, F. Grant

    2002-06-01

    Dissimilatory iron-reducing bacteria (DIRB) play an important role in regulating the aqueous geochemistry of iron and other metals in anaerobic, non-sulfidogenic groundwater environments; however, little work has directly assessed the cell surface electrochemistry of DIRB, or the nature of the interfacial environment around individual cells. The electrochemical properties of particulate solids are often inferred from titrations in which net surface charge is determined, assuming electroneutrality, as the difference between known added amounts of acid and base and measured proton concentration. The resultant titration curve can then be fit to a speciation model for the system to determine pKa values and site densities of reactive surface sites. Moreover, with the development of non-contact electrostatic force microscopy (EFM), it is now possible to directly inspect and quantify charge development on surfaces. A combination of acid-base titrations and EFM are being used to assess the electrochemical surface properties of the groundwater DIRB, Shewanella putrefaciens. The pKa spectra and EFM data show together that a high degree of electrochemical heterogeneity exists within the cell wall and at the cell surface of S. putrefaciens. Recognition of variations in the nature and spatial distribution of reactive sites that contribute to charge development on these bacteria implies further that the cell surface of these Fe(III)-reducing bacteria functions as a highly differentiated interfacial system capable of supporting multiple intermolecular interactions with both solutes and solids. These include surface complexation reactions involving dissolved metals, as well as adherence to mineral substrates such as hydrous ferric oxide through longer-range electrostatic interactions, and surface precipitation of secondary reduced-iron minerals.

  4. Tumor reactive stroma in cholangiocarcinoma: The fuel behind cancer aggressiveness

    PubMed Central

    Brivio, Simone; Cadamuro, Massimiliano; Strazzabosco, Mario; Fabris, Luca

    2017-01-01

    Cholangiocarcinoma (CCA) is a highly aggressive epithelial malignancy still carrying a dismal prognosis, owing to early lymph node metastatic dissemination and striking resistance to conventional chemotherapy. Although mechanisms underpinning CCA progression are still a conundrum, it is now increasingly recognized that the desmoplastic microenvironment developing in conjunction with biliary carcinogenesis, recently renamed tumor reactive stroma (TRS), behaves as a paramount tumor-promoting driver. Indeed, once being recruited, activated and dangerously co-opted by neoplastic cells, the cellular components of the TRS (myofibroblasts, macrophages, endothelial cells and mesenchymal stem cells) continuously rekindle malignancy by secreting a huge variety of soluble factors (cyto/chemokines, growth factors, morphogens and proteinases). Furthermore, these factors are long-term stored within an abnormally remodeled extracellular matrix (ECM), which in turn can deleteriously mold cancer cell behavior. In this review, we will highlight evidence for the active role played by reactive stromal cells (as well as by the TRS-associated ECM) in CCA progression, including an overview of the most relevant TRS-derived signals possibly fueling CCA cell aggressiveness. Hopefully, a deeper knowledge of the paracrine communications reciprocally exchanged between cancer and stromal cells will steer the development of innovative, combinatorial therapies, which can finally hinder the progression of CCA, as well as of other cancer types with abundant TRS, such as pancreatic and breast carcinomas.

  5. Effects of fuel type, driving cycle, and emission status on in-use vehicle exhaust reactivity.

    PubMed

    Ho, J; Winer, A M

    1998-07-01

    The introduction of reformulated gasolines significantly reduced exhaust hydrocarbon (HC) mass emissions, but few data are available concerning how these new fuels affect exhaust reactivity. Similarly, while it is well established that high-emitting vehicles contribute a significant portion of total mobile source HC mass emissions, it is also important to evaluate the exhaust reactivity from these vehicles. The objective of this study was to evaluate the relative influence on in-use vehicle exhaust reactivity of three critical factors: fuel, driving cycle, and vehicle emission status. Nineteen in-use vehicles were tested with seven randomly assigned fuel types and two driving cycles: the Federal Test Procedure (FTP) and the Unified Cycle (UC). Total exhaust reactivity was not statistically different between the FTP and UC cycles but was significantly affected by fuel type. On average, the exhaust reactivity for California Phase 2 fuel was the lowest (16% below the highest fuel type) among the seven fuels tested for cold start emissions. The average exhaust reactivity for high-emitting vehicles was significantly higher for hot stabilized (11%) and hot start (15%) emissions than for low-emitting vehicles. The exhaust reactivities for the FTP and UC cycles for light-end HCs and carbonyls were significantly different for the hot stabilized mode. There was a significant fuel effect on the mean specific reactivity (SR) for the mid-range HCs, but not for light-end HCs or carbonyls, while vehicle emission status affected the mean SR for all three HC compound classes.

  6. Molten salt extraction of transuranic and reactive fission products from used uranium oxide fuel

    SciTech Connect

    Herrmann, Steven Douglas

    2014-05-27

    Used uranium oxide fuel is detoxified by extracting transuranic and reactive fission products into molten salt. By contacting declad and crushed used uranium oxide fuel with a molten halide salt containing a minor fraction of the respective uranium trihalide, transuranic and reactive fission products partition from the fuel to the molten salt phase, while uranium oxide and non-reactive, or noble metal, fission products remain in an insoluble solid phase. The salt is then separated from the fuel via draining and distillation. By this method, the bulk of the decay heat, fission poisoning capacity, and radiotoxicity are removed from the used fuel. The remaining radioactivity from the noble metal fission products in the detoxified fuel is primarily limited to soft beta emitters. The extracted transuranic and reactive fission products are amenable to existing technologies for group uranium/transuranic product recovery and fission product immobilization in engineered waste forms.

  7. Reactive metabolites of desipramine and clomipramine: The kinetics of formation and reactivity with DNA.

    PubMed

    Korobkova, Ekaterina A; Nemeth, John; Cadougan, Mikeisha; Venkatratnam, Abhishek; Bassit, Mohanram; Azar, Nikolay

    2012-01-01

    Tricyclic antidepressants (TCAs), along with phenothyazines and some industrial chemicals, are shown to react with enzymes that exhibit peroxidase activity. These reactions result in the formation of reactive intermediates having unpaired electrons. The peroxidase oxidation and reactivity of two TCAs, desipramine and clomipramine, were investigated. As a model of peroxidase, horseradish peroxidase (HRP) was employed. The products of the peroxidase catalyzed oxidation of desipramine and clomipramine were identified as N-dealkylated compounds iminodibenzyl and 3-chloroiminodibenzyl using the GC/MS technique. Both drugs formed broad UV/vis absorption spectra in the presence of HRP and H(2)O(2), indicating the formation of a radical cations-reactive intermediate of the oxidation reaction. The dynamics of the formation of the desipramine intermediate was studied using UV/vis spectroscopy. The extinction coefficient was measured for the reactive intermediate, 7.80×10(3)M(-1)cm(-1), as well as the apparent Michaelis-Menten and catalytic constants, 4.4mM and 2.3s(-1), respectively. Both desipramine and clomipramine degraded DNA in the presence of HRP/H(2)O(2), as was revealed by agarose gel electrophoresis and PCI extraction. Manipulating the kinetic parameters of drug's radical formation and determining the extent of degradation to biomolecules could be potentially used for designing effective agents exhibiting specific reactivity.

  8. [Formation of reactive oxygen species during pollen grain germination].

    PubMed

    Smirnova, A V; Matveeva, N P; Polesskaia, O G; Ermakov, I P

    2009-01-01

    The formation of reactive oxygen species in pollen at the early germination stage, which precedes the formation of the pollen tube, was studied. During this period, pollen grain is being hydrated, abruptly increasing its volume, and it passes from the resting state to active metabolism. Fluorescent methods have made it possible to reveal reactive oxygen species in the cytoplasm and inner layer of the pollen wall, intine. The cytoplasmic reactive oxygen species were mostly found in mitochondria, while extracellular ones were localized in aperture zones of intine, as well as in the solution surrounding pollen grains in vitro. The content of extracellular reactive oxygen species decreased after superoxide dismutase (100 units per ml) and diphenylene iodonium (100 microM), which indicates NADPH oxidase as one of possible producent of them. In conditions of suppression of extracellular reactive oxygen species production (100 microM diphenilene iodonium) or their promoted removal (after addition of 10 to 100 microM ascorbic acid), the number of germinating pollen grains increased. This effect disappeared after further increase in the concentration of the listed reagents. The result is evidence of the significance of processes of generation/removal of extracellular reactive oxygen species for pollen germination.

  9. Oxidation and Gum Formation in Diesel Fuels.

    DTIC Science & Technology

    2014-09-26

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  10. Sensitivity and uncertainty analysis of reactivities for UO2 and MOX fueled PWR cells

    SciTech Connect

    Foad, Basma; Takeda, Toshikazu

    2015-12-31

    The purpose of this paper is to apply our improved method for calculating sensitivities and uncertainties of reactivity responses for UO{sub 2} and MOX fueled pressurized water reactor cells. The improved method has been used to calculate sensitivity coefficients relative to infinite dilution cross-sections, where the self-shielding effect is taken into account. Two types of reactivities are considered: Doppler reactivity and coolant void reactivity, for each type of reactivity, the sensitivities are calculated for small and large perturbations. The results have demonstrated that the reactivity responses have larger relative uncertainty than eigenvalue responses. In addition, the uncertainty of coolant void reactivity is much greater than Doppler reactivity especially for large perturbations. The sensitivity coefficients and uncertainties of both reactivities were verified by comparing with SCALE code results using ENDF/B-VII library and good agreements have been found.

  11. Sensitivity and uncertainty analysis of reactivities for UO2 and MOX fueled PWR cells

    NASA Astrophysics Data System (ADS)

    Foad, Basma; Takeda, Toshikazu

    2015-12-01

    The purpose of this paper is to apply our improved method for calculating sensitivities and uncertainties of reactivity responses for UO2 and MOX fueled pressurized water reactor cells. The improved method has been used to calculate sensitivity coefficients relative to infinite dilution cross-sections, where the self-shielding effect is taken into account. Two types of reactivities are considered: Doppler reactivity and coolant void reactivity, for each type of reactivity, the sensitivities are calculated for small and large perturbations. The results have demonstrated that the reactivity responses have larger relative uncertainty than eigenvalue responses. In addition, the uncertainty of coolant void reactivity is much greater than Doppler reactivity especially for large perturbations. The sensitivity coefficients and uncertainties of both reactivities were verified by comparing with SCALE code results using ENDF/B-VII library and good agreements have been found.

  12. Two-Dimensional Diffusion Theory Analysis of Reactivity Effects of a Fuel-Plate-Removal Experiment

    NASA Technical Reports Server (NTRS)

    Gotsky, Edward R.; Cusick, James P.; Bogart, Donald

    1959-01-01

    Two-dimensional two-group diffusion calculations were performed on the NASA reactor simulator in order to evaluate the reactivity effects of fuel plates removed successively from the center experimental fuel element of a seven- by three-element core loading at the Oak Ridge Bulk Shielding Facility. The reactivity calculations were performed by two methods: In the first, the slowing-down properties of the experimental fuel element were represented by its infinite media parameters; and, in the second, the finite size of the experimental fuel element was recognized, and the slowing-down properties of the surrounding core were attributed to this small region. The latter calculation method agreed very well with the experimented reactivity effects; the former method underestimated the experimental reactivity effects.

  13. FORMATION PROCESSES AND CONSEQUENCES OF REACTIVE AND NON-REACTIVE MINERAL PRECIPITATES IN PERMEABLE REACTIVE BARRIERS

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., change in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction, ...

  14. Reactivity-controlled compression ignition drive cycle emissions and fuel economy estimations using vehicle system simulations

    SciTech Connect

    Curran, Scott J.; Gao, Zhiming; Wagner, Robert M.

    2014-12-22

    In-cylinder blending of gasoline and diesel to achieve reactivity-controlled compression ignition has been shown to reduce NOX and soot emissions while maintaining or improving brake thermal efficiency as compared with conventional diesel combustion. The reactivity-controlled compression ignition concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load, allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. In this paper, a multi-mode reactivity-controlled compression ignition strategy is employed where the engine switches from reactivity-controlled compression ignition to conventional diesel combustion when speed and load demand are outside of the experimentally determined reactivity-controlled compression ignition range. The potential for reactivity-controlled compression ignition to reduce drive cycle fuel economy and emissions is not clearly understood and is explored here by simulating the fuel economy and emissions for a multi-mode reactivity-controlled compression ignition–enabled vehicle operating over a variety of US drive cycles using experimental engine maps for multi-mode reactivity-controlled compression ignition, conventional diesel combustion, and a 2009 port-fuel injected gasoline engine. Drive cycle simulations are completed assuming a conventional mid-size passenger vehicle with an automatic transmission. Multi-mode reactivity-controlled compression ignition fuel economy simulation results are compared with the same vehicle powered by a representative 2009 port-fuel injected gasoline engine over multiple drive cycles. Finally, engine-out drive cycle emissions are compared with conventional diesel combustion, and observations regarding relative gasoline and diesel tank sizes needed for the various drive cycles are also summarized.

  15. Reactivity-controlled compression ignition drive cycle emissions and fuel economy estimations using vehicle system simulations

    DOE PAGES

    Curran, Scott J.; Gao, Zhiming; Wagner, Robert M.

    2014-12-22

    In-cylinder blending of gasoline and diesel to achieve reactivity-controlled compression ignition has been shown to reduce NOX and soot emissions while maintaining or improving brake thermal efficiency as compared with conventional diesel combustion. The reactivity-controlled compression ignition concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load, allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. In this paper, a multi-mode reactivity-controlled compression ignition strategy is employed where the engine switches from reactivity-controlled compression ignition to conventional diesel combustion whenmore » speed and load demand are outside of the experimentally determined reactivity-controlled compression ignition range. The potential for reactivity-controlled compression ignition to reduce drive cycle fuel economy and emissions is not clearly understood and is explored here by simulating the fuel economy and emissions for a multi-mode reactivity-controlled compression ignition–enabled vehicle operating over a variety of US drive cycles using experimental engine maps for multi-mode reactivity-controlled compression ignition, conventional diesel combustion, and a 2009 port-fuel injected gasoline engine. Drive cycle simulations are completed assuming a conventional mid-size passenger vehicle with an automatic transmission. Multi-mode reactivity-controlled compression ignition fuel economy simulation results are compared with the same vehicle powered by a representative 2009 port-fuel injected gasoline engine over multiple drive cycles. Finally, engine-out drive cycle emissions are compared with conventional diesel combustion, and observations regarding relative gasoline and diesel tank sizes needed for the various drive cycles are also summarized.« less

  16. Premixed direct injection nozzle for highly reactive fuels

    DOEpatents

    Ziminsky, Willy Steve; Johnson, Thomas Edward; Lacy, Benjamin Paul; York, William David; Uhm, Jong Ho; Zuo, Baifang

    2013-09-24

    A fuel/air mixing tube for use in a fuel/air mixing tube bundle is provided. The fuel/air mixing tube includes an outer tube wall extending axially along a tube axis between an inlet end and an exit end, the outer tube wall having a thickness extending between an inner tube surface having a inner diameter and an outer tube surface having an outer tube diameter. The tube further includes at least one fuel injection hole having a fuel injection hole diameter extending through the outer tube wall, the fuel injection hole having an injection angle relative to the tube axis. The invention provides good fuel air mixing with low combustion generated NOx and low flow pressure loss translating to a high gas turbine efficiency, that is durable, and resistant to flame holding and flash back.

  17. Fuel composition and secondary organic aerosol formation: gas-turbine exhaust and alternative aviation fuels.

    PubMed

    Miracolo, Marissa A; Drozd, Greg T; Jathar, Shantanu H; Presto, Albert A; Lipsky, Eric M; Corporan, Edwin; Robinson, Allen L

    2012-08-07

    A series of smog chamber experiments were performed to investigate the effects of fuel composition on secondary particulate matter (PM) formation from dilute exhaust from a T63 gas-turbine engine. Tests were performed at idle and cruise loads with the engine fueled on conventional military jet fuel (JP-8), Fischer-Tropsch synthetic jet fuel (FT), and a 50/50 blend of the two fuels. Emissions were sampled into a portable smog chamber and exposed to sunlight or artificial UV light to initiate photo-oxidation. Similar to previous studies, neat FT fuel and a 50/50 FT/JP-8 blend reduced the primary particulate matter emissions compared to neat JP-8. After only one hour of photo-oxidation at typical atmospheric OH levels, the secondary PM production in dilute exhaust exceeded primary PM emissions, except when operating the engine at high load on FT fuel. Therefore, accounting for secondary PM production should be considered when assessing the contribution of gas-turbine engine emissions to ambient PM levels. FT fuel substantially reduced secondary PM formation in dilute exhaust compared to neat JP-8 at both idle and cruise loads. At idle load, the secondary PM formation was reduced by a factor of 20 with the use of neat FT fuel, and a factor of 2 with the use of the blend fuel. At cruise load, the use of FT fuel resulted in no measured formation of secondary PM. In every experiment, the secondary PM was dominated by organics with minor contributions from sulfate when the engine was operated on JP-8 fuel. At both loads, FT fuel produces less secondary organic aerosol than JP-8 because of differences in the composition of the fuels and the resultant emissions. This work indicates that fuel reformulation may be a viable strategy to reduce the contribution of emissions from combustion systems to secondary organic aerosol production and ultimately ambient PM levels.

  18. Intermediate Depth Earthquakes in Middle America: Fault Reactivation or Formation?

    NASA Astrophysics Data System (ADS)

    Langstaff, M. A.; Warren, L. M.; Silver, P. G.

    2006-12-01

    Intermediate-depth earthquakes are often attributed to dehydration embrittlement reactivating pre-existing weak zones. The orientations of pre-subduction faults are particularly well known offshore of Middle America, where seismic reflection profiles show outer-rise faults dipping towards the trench and extending >20~km into the lithosphere. If water is transported along these faults and incorporated into hydrous minerals, the faults may be reactivated later when the minerals dehydrate. In this case, the fault orientations should be the same in the outer rise and at depth, after accounting for the angle of subduction. To test this hypothesis, we analyze the directivity of 54 large (M_W > 5.7) earthquakes between 40--220~km depth in the Middle America Trench. For 15 of these earthquakes, the directivity vector allows us to confidently distinguish the fault plane of the earthquake. Between 40--85~km depth, we observe both subhorizontal and subvertical fault planes. The subvertical fault planes are consistent with the reactivation of outer rise faults, whereas the subhorizontal fault planes suggest the formation of new faults. Deeper than 85~km, we only observe subhorizontal faults, indicating that the outer rise faults are no longer reactivated. The occurrence of only subhorizontal faults may be due to unbending stresses preferentially creating horizontal faults, or an isobaric rupture process.

  19. Formation of protein S-nitrosylation by reactive oxygen species.

    PubMed

    Hlaing, K Htet; Clément, M-V

    2014-09-01

    In the present study, the formation of whole cellular S-nitrosylated proteins (protein-SNOs) by the reactive oxygen species (ROS), hydrogen peroxide (H2O2), and superoxide (O2(•-)) is demonstrated. A spectrum of protein cysteine oxidative modifications was detected upon incubation of serum-starved mouse embryonic fibroblasts with increasing concentrations of exogenous H2O2, ranging from exclusive protein-SNOs at low concentrations to a mixture of protein-SNOs and other protein oxidation at higher concentrations to exclusively non-SNO protein oxidation at the highest concentrations of the oxidant used. Furthermore, formation of protein-SNOs was also detected upon inhibition of the antioxidant protein Cu/Zn superoxide dismutase that results in an increase in intracellular concentration of O2(•-). These results were further validated using the phosphatase and tensin homologue, PTEN, as a model of a protein sensitive to oxidative modifications. The formation of protein-SNOs by H2O2 and O2(•-) was prevented by the NO scavenger, c-PTIO, as well as the peroxinitrite decomposition catalyst, FETPPS, and correlated with the production or the consumption of nitric oxide (NO), respectively. These data suggest that the formation of protein-SNOs by H2O2 or O2(•-) requires the presence or the production of NO and involves the formation of the nitrosylating intermediate, peroxinitrite.

  20. Deposit formation and heat transfer in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Giovanetti, A. J.; Spadaccini, L. J.; Szetela, E. J.

    1983-01-01

    An experimental research program was undertaken to investigate the thermal stability and heat transfer characteristics of several hydrocarbon fuels under conditions that simulate high-pressure, rocket engine cooling systems. The rates of carbon deposition in heated copper and nickel-plated copper tubes were determined for RP-1, propane, and natural gas using a continuous flow test apparatus which permitted independent variation and evaluation of the effect on deposit formation of wall temperature, fuel pressure, and fuel velocity. In addition, the effects of fuel additives and contaminants, cryogenic fuel temperatures, and extended duration testing with intermittent operation were examined. Parametric tests to map the thermal stability characteristics of RP-1, commercial-grade propane, and natural gas were conducted at pressures of 6.9 to 13.8 MPa, bulk fuel velocities of 30 to 90 m/s, and tube wall temperatures in the range of 230 to 810 K. Also, tests were run in which propane and natural gas fuels were chilled to 230 and 160 K, respectively. Corrosion of the copper tube surface was detected for all fuels tested. Plating the inside of the copper tubes with nickel reduced deposit formation and eliminated tube corrosion in most cases. The lowest rates of carbon deposition were obtained for natural gas, and the highest rates were obtained for propane. For all fuels tested, the forced-convection heat transfer film coefficients were satisfactorily correlated using a Nusselt-Reynolds-Prandtl number equation.

  1. Soot-driven reactive oxygen species formation from incense burning.

    PubMed

    Chuang, Hsiao-Chi; Jones, Tim P; Lung, Shih-Chun C; BéruBé, Kelly A

    2011-10-15

    This study investigated the effects of reactive oxygen species (ROS) generated as a function of the physicochemistry of incense particulate matter (IPM), diesel exhaust particles (DEP) and carbon black (CB). Microscopical and elemental analyses were used to determine particle morphology and inorganic compounds. ROS was determined using the reactive dye, Dichlorodihydrofluorescin (DCFH), and the Plasmid Scission Assay (PSA), which determine DNA damage. Two common types of soot were observed within IPM, including nano-soot and micro-soot, whereas DEP and CB mainly consisted of nano-soot. These PM were capable of causing oxidative stress in a dose-dependent manner, especially IPM and DEP. A dose of IPM (36.6-102.3μg/ml) was capable of causing 50% oxidative DNA damage. ROS formation was positively correlated to smaller nano-soot aggregates and bulk metallic compounds, particularly Cu. These observations have important implications for respiratory health given that inflammation has been recognised as an important factor in the development of lung injury/diseases by oxidative stress. This study supports the view that ROS formation by combustion-derived PM is related to PM physicochemistry, and also provides new data for IPM.

  2. Impact investigation of reactor fuel operating parameters on reactivity for use in burnup credit applications

    NASA Astrophysics Data System (ADS)

    Sloma, Tanya Noel

    When representing the behavior of commercial spent nuclear fuel (SNF), credit is sought for the reduced reactivity associated with the net depletion of fissile isotopes and the creation of neutron-absorbing isotopes, a process that begins when a commercial nuclear reactor is first operated at power. Burnup credit accounts for the reduced reactivity potential of a fuel assembly and varies with the fuel burnup, cooling time, and the initial enrichment of fissile material in the fuel. With regard to long-term SNF disposal and transportation, tremendous benefits, such as increased capacity, flexibility of design and system operations, and reduced overall costs, provide an incentive to seek burnup credit for criticality safety evaluations. The Nuclear Regulatory Commission issued Interim Staff Guidance 8, Revision 2 in 2002, endorsing burnup credit of actinide composition changes only; credit due to actinides encompasses approximately 30% of exiting pressurized water reactor SNF inventory and could potentially be increased to 90% if fission product credit were accepted. However, one significant issue for utilizing full burnup credit, compensating for actinide and fission product composition changes, is establishing a set of depletion parameters that produce an adequately conservative representation of the fuel's isotopic inventory. Depletion parameters can have a significant effect on the isotopic inventory of the fuel, and thus the residual reactivity. This research seeks to quantify the reactivity impact on a system from dominant depletion parameters (i.e., fuel temperature, moderator density, burnable poison rod, burnable poison rod history, and soluble boron concentration). Bounding depletion parameters were developed by statistical evaluation of a database containing reactor operating histories. The database was generated from summary reports of commercial reactor criticality data. Through depletion calculations, utilizing the SCALE 6 code package, several light

  3. NOx formation in combustion of gaseous fuel in ejection burner

    NASA Astrophysics Data System (ADS)

    Rimár, Miroslav; Kulikov, Andrii

    2016-06-01

    The aim of this work is to prepare model for researching of the formation in combustion of gaseous fuels. NOx formation is one of the main ecological problems nowadays as nitrogen oxides is one of main reasons of acid rains. The ANSYS model was designed according to the calculation to provide full combustion and good mixing of the fuel and air. The current model is appropriate to research NOx formation and the influence of the different principles of NOx reduction method. Applying of designed model should spare both time of calculations and research and also money as you do not need to measure the burner characteristics.

  4. A Critical Review of Practice of Equating the Reactivity of Spent Fuel to Fresh Fuel in Burnup Credit Criticality Safety Analyses for PWR Spent Fuel Pool Storage

    SciTech Connect

    Wagner, J.C.; Parks, C.V.

    2000-09-01

    This research examines the practice of equating the reactivity of spent fuel to that of fresh fuel for the purpose of performing burnup credit criticality safety analyses for PWR spent fuel pool (SFP) storage conditions. The investigation consists of comparing k{sub inf} estimates based on reactivity equivalent fresh fuel enrichment (REFFE) to k{sub inf} estimates using the actual spent fuel isotopics. Analyses of selected storage configurations common in PWR SFPs show that this practice yields nonconservative results (on the order of a few tenths of a percent) in configurations in which the spent fuel is adjacent to higher-reactivity assemblies (e.g., fresh or lower-burned assemblies) and yields conservative results in configurations in which spent fuel is adjacent to lower-reactivity assemblies (e.g., higher-burned fuel or empty cells). When the REFFE is determined based on unborated water moderation, analyses for storage conditions with soluble boron present reveal significant nonconservative results associated with the use of the REFFE. This observation is considered to be important, especially considering the recent allowance of credit for soluble boron up to 5% in reactivity. Finally, it is shown that the practice of equating the reactivity of spent fuel to fresh fuel is acceptable, provided the conditions for which the REFFE was determined remain unchanged. Determination of the REFFE for a reference configuration and subsequent use of the REFFE for different configurations violates the basis used for the determination of the REFFE and, thus, may lead to inaccurate, and possibly, nonconservative estimates of reactivity. A significant concentration ({approximately}2000 ppm) of soluble boron is typically (but not necessarily required to be) present in PWR SFPs, of which only a portion ({le} 500 ppm) may be credited in safety analyses. Thus, a large subcritical margin currently exists that more than accounts for errors or uncertainties associated with the use of

  5. Deposit formation and heat transfer in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Giovanetti, A. J.; Spadaccini, L. J.; Szetela, E. J.

    1984-01-01

    An experimental research program was undertaken to investigate the thermal stability and heat transfer characteristics of several hydrocarbon fuels under conditions that simulate high-pressure, rocket engine cooling systems. The rates of carbon deposition in heated copper and nickel-plated copper tubes were determined for RP-1, propane, and natural gas using a continuous flow test apparatus which permitted independent variation and evaluation of the effect on deposit formation of wall temperature, fuel pressure, and fuel velocity. In addition, the effects of fuel additives and contaminants, cryogenic fuel temperatures, and extended duration testing with intermittent operation were examined. Corrosion of the copper tube surface was detected for all fuels tested; however, plating the insides of the tubes with nickel reduced deposit formation and eliminated corrosion in most cases. The lowest rates of carbon deposition were obtained for natural gas, and the highest rates were obtained for propane. Forced-convection heat transfer film coefficients were satisfactorily correlated using a Nusselt-Reynolds-Prandtl number equation for all the fuels tested.

  6. Outflow channel sources, reactivation, and chaos formation, Xanthe Terra, Mars

    USGS Publications Warehouse

    Rodriguez, J.A.P.; Sasaki, S.; Kuzmin, R.O.; Dohm, J.M.; Tanaka, K.L.; Miyamoto, H.; Kurita, K.; Komatsu, G.; Fairen, A.G.; Ferris, J.C.

    2005-01-01

    The undulating, warped, and densely fractured surfaces of highland regions east of Valles Marineris (located north of the eastern Aureum Chaos, east of the Hydraotes Chaos, and south of the Hydaspis Chaos) resulted from extensional surface warping related to ground subsidence, caused when pressurized water confined in subterranean caverns was released to the surface. Water emanations formed crater lakes and resulted in channeling episodes involved in the excavation of Ares, Tiu, and Simud Valles of the eastern part of the circum-Chryse outflow channel system. Progressive surface subsidence and associated reduction of the subsurface cavernous volume, and/or episodes of magmatic-driven activity, led to increases of the hydrostatic pressure, resulting in reactivation of both catastrophic and non-catastrophic outflow activity. Ancient cratered highland and basin materials that underwent large-scale subsidence grade into densely fractured terrains. Collapse of rock materials in these regions resulted in the formation of chaotic terrains, which occur in and near the headwaters of the eastern circum-Chryse outflow channels. The deepest chaotic terrain in the Hydaspis Chaos region resulted from the collapse of pre-existing outflow channel floors. The release of volatiles and related collapse may have included water emanations not necessarily linked to catastrophic outflow. Basal warming related to dike intrusions, thermokarst activity involving wet sediments and/or dissected ice-enriched country rock, permafrost exposed to the atmosphere by extensional tectonism and channel incision, and/or the injection of water into porous floor material, may have enhanced outflow channel floor instability and subsequent collapse. In addition to the possible genetic linkage to outflow channel development dating back to at least the Late Noachian, clear disruption of impact craters with pristine ejecta blankets and rims, as well as preservation of fine tectonic fabrics, suggest that

  7. 40 CFR 600.302-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Fuel economy label format requirements...) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Labeling § 600.302-08 Fuel economy label format requirements. Examples of fuel economy labels for gasoline...

  8. ReaxFF Reactive Force-Field Modeling of the Triple-Phase Boundary in a Solid Oxide Fuel Cell.

    PubMed

    Merinov, Boris V; Mueller, Jonathan E; van Duin, Adri C T; An, Qi; Goddard, William A

    2014-11-20

    In our study, the Ni/YSZ ReaxFF reactive force field was developed by combining the YSZ and Ni/C/H descriptions. ReaxFF reactive molecular dynamics (RMD) were applied to model chemical reactions, diffusion, and other physicochemical processes at the fuel/Ni/YSZ interface. The ReaxFF RMD simulations were performed on the H2/Ni/YSZ and C4H10/Ni/YSZ triple-phase boundary (TPB) systems at 1250 and 2000 K, respectively. The simulations indicate amorphization of the Ni surface, partial decohesion (delamination) at the interface, and coking, which have indeed all been observed experimentally. They also allowed us to derive the mechanism of the butane conversion at the Ni/YSZ interface. Many steps of this mechanism are similar to the pyrolysis of butane. The products obtained in our simulations are the same as those in experiment, which indicates that the developed ReaxFF potential properly describes complex physicochemical processes, such as the oxide-ion diffusion, fuel conversion, water formation reaction, coking, and delamination, occurring at the TPB and can be recommended for further computational studies of the fuel/electrode/electrolyte interfaces in a SOFC.

  9. Reduced-reactivity-swing LEU fuel cycle analyses for HFR Petten

    SciTech Connect

    Deen, J.R.; Snelgrove, J.L.

    1985-01-01

    The primary objective of these low enriched uranium (LEU) fuel cycle analyses was to effect at least a 33% reduction in the reactivity swing now experienced in the high enriched uranium (HEU) cycle while minimizing increases in /sup 235/U loading and power peaking. All LEU equilibrium fuel cycle calculations were performed using either a 19- or 20-plate fuel element with 0.76-mm-thick meat and 0.5- or 0.6-mm-thick Cd wires as burnable absorbers and 16- or 17-plate control rod fuel followers with 0.76-mm-thick meat. Burnup-dependent microscopic cross sections were used for all heavy metals and fission products. A three-dimensional model was used to account for the effect of partially inserted control rods upon burnup profiles of fuel and of burnable absorbers and upon power peaking. The equilibrium cycle reactivity swing (or, equivalently control rod movement) was reduced by 50% using LEU fuel with U meat densities <4.8 Mg/m/sup 3/. 6 refs., 4 tabs.

  10. A microfluidic direct formate fuel cell on paper.

    PubMed

    Copenhaver, Thomas S; Purohit, Krutarth H; Domalaon, Kryls; Pham, Linda; Burgess, Brianna J; Manorothkul, Natalie; Galvan, Vicente; Sotez, Samantha; Gomez, Frank A; Haan, John L

    2015-08-01

    We describe the first direct formate fuel cell on a paper microfluidic platform. In traditional membrane-less microfluidic fuel cells (MFCs), external pumping consumes power produced by the fuel cell in order to maintain co-laminar flow of the anode stream and oxidant stream to prevent mixing. However, in paper microfluidics, capillary action drives flow while minimizing stream mixing. In this work, we demonstrate a paper MFC that uses formate and hydrogen peroxide as the anode fuel and cathode oxidant, respectively. Using these materials we achieve a maximum power density of nearly 2.5 mW/mg Pd. In a series configuration, our MFC achieves an open circuit voltage just over 1 V, and in a parallel configuration, short circuit of 20 mA absolute current. We also demonstrate that the MFC does not require continuous flow of fuel and oxidant to produce power. We found that we can pre-saturate the materials on the paper, stop the electrolyte flow, and still produce approximately 0.5 V for 15 min. This type of paper MFC has potential applications in point-of-care diagnostic devices and other electrochemical sensors.

  11. Flame extinction limit and particulates formation in fuel blends

    NASA Astrophysics Data System (ADS)

    Subramanya, Mahesh

    Many fuels used in material processing and power generation applications are generally a blend of various hydrocarbons. Although the combustion and aerosol formation dynamics of individual fuels is well understood, the flame dynamics of fuel blends are yet to be characterized. This research uses a twin flame counterflow burner to measure flame velocity, flame extinction, particulate formation and particulate morphology of hydrogen fuel blend flames at different H2 concentration, oscillation frequencies and stretch conditions. Phase resolved spectroscopic measurements (emission spectra) of OH, H, O and CH radical/atom concentrations is used to characterize the heat release processes of the flame. In addition flame generated particulates are collected using thermophoretic sample technique and are qualitative analyzed using Raman Spectroscopy and SEM. Such measurements are essential for the development of advanced computational tools capable of predicting fuel blend flame characteristics at realistic combustor conditions. The data generated through the measurements of this research are representative, and yet accurate, with unique well defined boundary conditions which can be reproduced in numerical computations for kinetic code validations.

  12. Oxidation and formation of deposit precursors in hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Mayo, F. R.; Lan, B.; Cotts, D. B.; Buttrill, S. E., Jr.; St.john, G. A.

    1983-01-01

    The oxidation of two jet turbine fuels and some pure hydrocarbons was studied at 130 C with and without the presence of small amounts of N-methyl pyrrole (NMP) or indene. Tendency to form solid-deposit precursors was studied by measuring soluble gum formation as well as dimer and trimer formation using field ionization mass spectrometry. Pure n-dodecane oxidized fastest and gave the smallest amount of procursors. An unstable fuel oil oxidized much slower but formed large amounts of precursors. Stable Jet A fuel oxidized slowest and gave little precursors. Indene either retarded or accelerated the oxidation of n-dodecane, depending on its concentration, but always caused more gum formation. The NMP greatly retarded n-dodecane oxidation but accelerated Jet A oxidation and greatly increased the latter's gum formation. In general, the additive reacted faster and formed most of the gum. Results are interpreted in terms of classical cooxidation theory. The effect of oxygen pressure on gum formation is also reported.

  13. Gum and deposit formation from jet turbine and diesel fuels

    SciTech Connect

    Mayo, F.R.; Lan, B.Y.

    1983-09-01

    The objective of this work is to determine the chemistry of deposit formation in hot parts of jet turbine and diesel engines and, thus, to predict and prevent deposit formation. Previous work in the field has been extensive, but a real understanding of deposit formation has been elusive. Work at SRI started on the basis that deposit formation from fuels must take place stepwise and is associated with autoxidation and the hydroperoxide produced. More recent work showed that in the absence of dissolved oxygen, higher temperatures are required for deposit formation. A recent report indicated that gum and deposit formation proceed mainly through oxidation products of the parent hydrocarbon, coupling of these products to dimeric, trimeric and higher condensation products (partly or wholly by radicals from hydroperoxides) and precipitation of insoluble products. The authors know of no information on how these first precipitates are converted to the ultimate, very insoluble, carbonaceous materials that cause engine problems. The present paper describes measurements of rates of oxidation and soluble gum formation in both pure hydrocarbons and mixed hydrocarbon fuels. Some patterns appear that can be largely explained on the basis of what is known about co-oxidations of hydrocarbon mixtures.

  14. CASMO5/TSUNAMI-3D spent nuclear fuel reactivity uncertainty analysis

    SciTech Connect

    Ferrer, R.; Rhodes, J.; Smith, K.

    2012-07-01

    The CASMO5 lattice physics code is used in conjunction with the TSUNAMI-3D sequence in ORNL's SCALE 6 code system to estimate the uncertainties in hot-to-cold reactivity changes due to cross-section uncertainty for PWR assemblies at various burnup points. The goal of the analysis is to establish the multiplication factor uncertainty similarity between various fuel assemblies at different conditions in a quantifiable manner and to obtain a bound on the hot-to-cold reactivity uncertainty over the various assembly types and burnup attributed to fundamental cross-section data uncertainty. (authors)

  15. Impacts of fuel formulation and engine operating parameters on the nanostructure and reactivity of diesel soot

    NASA Astrophysics Data System (ADS)

    Yehliu, Kuen

    This study focuses on the impacts of fuel formulations on the reactivity and nanostructure of diesel soot. A 2.5L, 4-cylinder, turbocharged, common rail, direct injection light-duty diesel engine was used in generating soot samples. The impacts of engine operating modes and the start of combustion on soot reactivity were investigated first. Based on preliminary investigations, a test condition of 2400 rpm and 64 Nm, with single and split injection strategies, was chosen for studying the impacts of fuel formulation on the characteristics of diesel soot. Three test fuels were used: an ultra low sulfur diesel fuel (BP15), a pure soybean methyl-ester (B100), and a synthetic Fischer-Tropsch fuel (FT) produced in a gas-to-liquid process. The start of injection (SOI) and fuel rail pressures were adjusted such that the three test fuels have similar combustion phasing, thereby facilitating comparisons between soots from the different fuels. Soot reactivity was investigated by thermogravimetric analysis (TGA). According to TGA, B100 soot exhibits the fastest oxidation on a mass basis followed by BP15 and FT derived soots in order of apparent rate constant. X-ray photoelectron spectroscopy (XPS) indicates no relation between the surface oxygen content and the soot reactivity. Crystalline information for the soot samples was obtained using X-ray diffraction (XRD). The basal plane diameter obtained from XRD was inversely related to the apparent rate constants for soot oxidation. For comparison, high resolution transmission electron microscopy (HRTEM) provided images of the graphene layers. Quantitative image analysis proceeded by a custom algorithm. B100 derived soot possessed the shortest mean fringe length and greatest mean fringe tortuosity. This suggests soot (nano)structural disorder correlates with a faster oxidation rate. Such results are in agreement with the X-ray analysis, as the observed fringe length is a measure of basal plane diameter. Moreover the relation

  16. Molecular dissection of reactive astrogliosis and glial scar formation

    PubMed Central

    Sofroniew, Michael V.

    2009-01-01

    Reactive astrogliosis, whereby astrocytes undergo varying molecular and morphological changes, is a ubiquitous but poorly understood hallmark of all central nervous system pathologies. Now genetic tools are enabling the molecular dissection of the functions and mechanisms of reactive astrogliosis in vivo. Recent studies provide compelling evidence that reactive astrogliosis may exert both beneficial and detrimental effects in a context-dependent manner determined by specific molecular signaling cascades. Reactive astrocytes may have both loss of normal functions and gain of abnormal effects that can feature prominently in a variety of disease processes. This article reviews developments in the signaling mechanisms that regulate specific aspects of reactive astrogliosis and highlights the potential to identify novel therapeutic molecular targets for diverse neurological disorders. PMID:19782411

  17. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    NASA Technical Reports Server (NTRS)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  18. Fabric-based alkaline direct formate microfluidic fuel cells.

    PubMed

    Domalaon, Kryls; Tang, Catherine; Mendez, Alex; Bernal, Franky; Purohit, Krutarth; Pham, Linda; Haan, John; Gomez, Frank A

    2017-01-12

    Fabric-based microfluidic fuel cells (MFCs) serve as a novel, cost-efficient alternative to traditional FCs and batteries, since fluids naturally travel across fabric via capillary action, eliminating the need for an external pump and lowering production and operation costs. Building on previous research with Y-shaped paper-based MFCs, fabric-based MFCs mitigate fragility and durability issues caused by long periods of fuel immersion. In this study, we describe a microfluidic fabric-based direct formate fuel cell, with 5 M potassium formate and 30% hydrogen peroxide as the anode fuel and cathode oxidant, respectively. Using a two-strip, stacked design, the optimized parameters include the type of encasement, the barrier, and the fabric type. Surface contact of the fabric and laminate sheet expedited flow and respective chemical reactions. The maximum current (22.83 mA/cm(2) ) and power (4.40 mW/cm(2) ) densities achieved with a 65% cotton/35% polyester blend material are a respective 8.7% and 32% higher than previous studies with Y-shaped paper-based MFCs. In series configuration, the MFCs generate sufficient energy to power a handheld calculator, a thermometer, and a spectrum of light-emitting diodes.

  19. 78 FR 8050 - Spent Fuel Cask Certificate of Compliance Format and Content

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-05

    ... COMMISSION 10 CFR Part 72 Spent Fuel Cask Certificate of Compliance Format and Content AGENCY: Nuclear... that governs the format and content of spent fuel storage cask Certificates of Compliance (CoCs... criteria for the format and content to be included in a spent fuel storage cask Certificate of...

  20. LOX/hydrocarbon fuel carbon formation and mixing data analysis

    NASA Technical Reports Server (NTRS)

    Fang, J.

    1983-01-01

    By applying the Priem-Heidmann Generalized-Length vaporization correlation, the computer model developed by the present study predicts the spatial variation of propellant vaporization rate using the injector cold flow results to define the streamtubes. The calculations show that the overall and local propellant vaporization rate and mixture ratio change drastically as the injection element type or the injector operating condition is changed. These results are compared with the regions of carbon formation observed in the photographic combustion testing. The correlation shows that the fuel vaporization rate and the local mixture ratio produced by the injector element have first order effects on the degree of carbon formation.

  1. Performance of Trasuranic-Loaded Fully Ceramic Micro-Encapsulated Fuel in LWRs Interim Report, Including Void Reactivity Evaluation

    SciTech Connect

    Michael A. Pope; Brian Boer; Gilles Youinou; Abderrafi M. Ougouag

    2011-03-01

    The current focus of the Deep Burn Project is on once-through burning of transuranice (TRU) in light water reactors (LWRs). The fuel form is called Fully-Ceramic Micro-encapsulated (FCM) fuel, a concept that borrows the tri-isotropic (TRISO) fuel particle design from high-temperature reactor technology. In the Deep Burn LWR (DB-LWR) concept, these fuel particles would be pressed into compacts using SiC matrix material and loaded into fuel pins for use in conventional LWRs. The TRU loading comes from the spent fuel of a conventional LWR after 5 years of cooling. Unit cell calculations have been performed using the DRAGON-4 code in order assess the physics attributes of TRU-only FCM fuel in an LWR lattice. Depletion calculations assuming an infinite lattice condition were performed with calculations of various reactivity coefficients performed at each step. Unit cells containing typical UO2 and MOX fuel were analyzed in the same way to provide a baseline against which to compare the TRU-only FCM fuel. Loading of TRU-only FCM fuel into a pin without significant quantities of uranium challenges the design from the standpoint of several key reactivity parameters, particularly void reactivity, and to some degree, the Doppler coefficient. These unit cells, while providing an indication of how a whole core of similar fuel would behave, also provide information of how individual pins of TRU-only FCM fuel would influence the reactivity behavior of a heterogeneous assembly. If these FCM fuel pins are included in a heterogeneous assembly with LEU fuel pins, the overall reactivity behavior would be dominated by the uranium pins while attractive TRU destruction performance of the TRU-only FCM fuel pins may be preserved. A configuration such as this would be similar to CONFU assemblies analyzed in previous studies. Analogous to the plutonium content limits imposed on MOX fuel, some amount of TRU-only FCM pins in an otherwise-uranium fuel assembly may give acceptable reactivity

  2. Technical Basis for Peak Reactivity Burnup Credit for BWR Spent Nuclear Fuel in Storage and Transportation Systems

    SciTech Connect

    Marshall, William BJ J; Ade, Brian J; Bowman, Stephen M; Gauld, Ian C; Ilas, Germina; Mertyurek, Ugur; Radulescu, Georgeta

    2015-01-01

    Oak Ridge National Laboratory and the United States Nuclear Regulatory Commission have initiated a multiyear project to investigate application of burnup credit for boiling-water reactor (BWR) fuel in storage and transportation casks. This project includes two phases. The first phase (1) investigates applicability of peak reactivity methods currently used in spent fuel pools (SFPs) to storage and transportation systems and (2) evaluates validation of both reactivity (keff) calculations and burnup credit nuclide concentrations within these methods. The second phase will focus on extending burnup credit beyond peak reactivity. This paper documents the first phase, including an analysis of lattice design parameters and depletion effects, as well as both validation components. Initial efforts related to extended burnup credit are discussed in a companion paper. Peak reactivity analyses have been used in criticality analyses for licensing of BWR fuel in SFPs over the last 20 years. These analyses typically combine credit for the gadolinium burnable absorber present in the fuel with a modest amount of burnup credit. Gadolinium burnable absorbers are used in BWR assemblies to control core reactivity. The burnable absorber significantly reduces assembly reactivity at beginning of life, potentially leading to significant increases in assembly reactivity for burnups less than 15–20 GWd/MTU. The reactivity of each fuel lattice is dependent on gadolinium loading. The number of gadolinium-bearing fuel pins lowers initial lattice reactivity, but it has a small impact on the burnup and reactivity of the peak. The gadolinium concentration in each pin has a small impact on initial lattice reactivity but a significant effect on the reactivity of the peak and the burnup at which the peak occurs. The importance of the lattice parameters and depletion conditions are primarily determined by their impact on the gadolinium depletion. Criticality code validation for BWR burnup

  3. Fuel Cell Manufacturing Diagnostic Techniques: IR Thermography with Reactive Flow through Excitation

    SciTech Connect

    Manak, A. J.; Ulsh, M.; Bender, G.

    2012-01-01

    While design and material considerations for PEMFCs have a large impact on cost, it is also necessary to consider a transition to high volume production of fuel cell systems, including MEA components, to enable economies of scale and reduce per unit cost. One of the critical manufacturing tasks is developing and deploying techniques to provide in‐process measurement of fuel cell components for quality control. This effort requires a subsidiary task: The study of the effect of manufacturing defects on performance and durability with the objective to establish validated manufacturing tolerances for fuel cell components. This work focuses on the development of a potential quality control method for gas diffusion electrodes (GDEs). The method consists of infrared (IR) thermography combined with reactive flow through (RFT) excitation. Detection of catalyst loading reduction defects in GDE catalyst layers will be presented.

  4. An improved alkaline direct formate paper microfluidic fuel cell.

    PubMed

    Galvan, Vicente; Domalaon, Kryls; Tang, Catherine; Sotez, Samantha; Mendez, Alex; Jalali-Heravi, Mehdi; Purohit, Krutarth; Pham, Linda; Haan, John; Gomez, Frank A

    2016-02-01

    Paper-based microfluidic fuel cells (MFCs) are a potential replacement for traditional FCs and batteries due to their low cost, portability, and simplicity to operate. In MFCs, separate solutions of fuel and oxidant migrate through paper due to capillary action and laminar flow and, upon contact with each other and catalyst, produce electricity. In the present work, we describe an improved microfluidic paper-based direct formate FC (DFFC) employing formate and hydrogen peroxide as the anode fuel and cathode oxidant, respectively. The dimensions of the lateral column, current collectors, and cathode were optimized. A maximum power density of 2.53 mW/cm(2) was achieved with a DFFC of surface area 3.0 cm(2) , steel mesh as current collector, 5% carbon to paint mass ratio for cathode electrode and, 30% hydrogen peroxide. The longevity of the MFC's detailed herein is greater than eight hours with continuous flow of streams. In a series configuration, the MFCs generate sufficient energy to power light-emitting diodes and a handheld calculator.

  5. Formation of dielectric silicon compounds by reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Veselov, D. S.; Voronov, Yu A.

    2016-09-01

    The paper is devoted to the study of reactive magnetron sputtering of the silicon target in the ambient of inert argon gas with reactive gas, nitrogen or oxygen. The magnetron was powered by two mid-frequency generators of a rectangular pulse of opposite polarity. The negative polarity pulse provides the sputtering of the target. The positive polarity pulse provides removal of accumulated charge from the surface of the target. This method does not require any special devices of resistances matching and provides continuous sputtering of the target.

  6. 40 CFR 600.307-95 - Fuel economy label format requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel economy label format requirements...) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Regulations for 1977 and Later Model Year Automobiles-Labeling § 600.307-95 Fuel economy label...

  7. 40 CFR 600.307-86 - Fuel economy label format requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel economy label format requirements...) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Regulations for 1977 and Later Model Year Automobiles-Labeling § 600.307-86 Fuel economy label...

  8. Non-destructive assay of spent nuclear fuel using passive neutron Albedo reactivity

    SciTech Connect

    Evans, L G; Schear, M A; Croft, S; Tobin, S J; Swinhoe, M T; Menlove, H O

    2010-01-01

    Passive Neutron Albedo Reactivity (PNAR) is one of fourteen techniques that has been researched and evaluated to form part of a comprehensive and integrated detection system for the non-destructive assay (NDA) of spent nuclear fuel. PNAR implemented with {sup 3}He tubes for neutron detection (PNAR-{sup 3}He) is the measurement of time correlated neutrons from a spent fuel assembly with and without a Cadmium (Cd) layer surrounding the assembly. PNAR utilizes the self-interrogation of the fuel via reflection of neutrons born in the fuel assembly back in to the fuel assembly. The neutrons originate primarily from spontaneous fission events within the fuel itself (Curium-244) but are amplified by multiplication. The presence and removal of the Cd provides two measurement conditions with different neutron energy spectra and therefore different interrogating neutron characteristics. Cd has a high cross-section of absorption for slow neutrons and therefore greatly reduces the low energy (thermal) neutron fluence rate returning. The ratios of the Singles, Doubles and Triples count rates obtained in each case are known as the Cd ratios, which are related to fissile content. A potential safeguards application for which PNAR-{sup 3}He is particularly suited is 'fingerprinting'. Fingerprinting could function as an alternative to plutonium (Pu) mass determination; providing confidence that material was not diverted during transport between sites. PNAR-{sup 3}He has six primary NDA signatures: Singles, Doubles and Triples count rates measured with two energy spectra at both shipping and receiving sites. This is to uniquely identify the fuel assembly, and confirm no changes have taken place during transport. Changes may indicate all attempt to divert material for example. Here, the physics of the PNAR-{sup 3}He concept will be explained, alongside a discussion on the development of a prototypical PNAR-{sup 3}He instrument using simulation. The capabilities and performance of the

  9. 40 CFR Appendix Viii to Part 600 - Fuel Economy Label Formats

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Fuel Economy Label Formats VIII... POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Pt. 600, App. VIII Appendix VIII to Part 600—Fuel Economy Label Formats EC01MY92.117 EC01MY92.118 EC01MY92.119...

  10. 40 CFR Appendix Viii to Part 600 - Fuel Economy Label Formats

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel Economy Label Formats VIII... POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Pt. 600, App. VIII Appendix VIII to Part 600—Fuel Economy Label Formats EC01MY92.117 EC01MY92.118 EC01MY92.119...

  11. Chemical reactivity testing for the National Spent Nuclear Fuel Program. Revision 2

    SciTech Connect

    Koester, L.W.

    2000-02-08

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, Y60-101PD, Quality Program Description, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted. The project consists of conducting three separate series of related experiments, ''Passivation of Uranium Hydride Powder With Oxygen and Water'', '''Passivation of Uranium Hydride Powder with Surface Characterization'', and ''Electrochemical Measure of Uranium Hydride Corrosion Rate''.

  12. Spent fuel measurements. passive neutron albedo reactivity (PNAR) and photon signatures

    SciTech Connect

    Eigenbrodt, Julia; Menlove, Howard Olsen

    2016-03-29

    The International Atomic Energy Agency’s (IAEA) safeguards technical objective is the timely detection of a diversion of a significant quantity of nuclear material from peaceful activities to the manufacture of nuclear weapons or of other nuclear explosive devices or for purposes unknown, and deterrence of such diversion by the risk of early detection. An important IAEA task towards meeting this objective is the ability to accurately and reliably measure spent nuclear fuel (SNF) to verify reactor operating parameters and verify that the fuel has not been removed from reactors or SNF storage facilities. This dissertation analyzes a method to improve the state-of-the-art of nuclear material safeguards measurements using two combined measurement techniques: passive neutron albedo reactivity (PNAR) and passive spectral photon measurements.

  13. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  14. Pebble Fuel Handling and Reactivity Control for Salt-Cooled High Temperature Reactors

    SciTech Connect

    Peterson, Per; Greenspan, Ehud

    2015-02-09

    This report documents the work completed on the X-PREX facility under NEUP Project 11- 3172. This project seeks to demonstrate the viability of pebble fuel handling and reactivity control for fluoride salt-cooled high-temperature reactors (FHRs). The research results also improve the understanding of pebble motion in helium-cooled reactors, as well as the general, fundamental understanding of low-velocity granular flows. Successful use of pebble fuels in with salt coolants would bring major benefits for high-temperature reactor technology. Pebble fuels enable on-line refueling and operation with low excess reactivity, and thus simpler reactivity control and improved fuel utilization. If fixed fuel designs are used, the power density of salt- cooled reactors is limited to 10 MW/m3 to obtain adequate duration between refueling, but pebble fuels allow power densities in the range of 20 to 30 MW/m3. This can be compared to the typical modular helium reactor power density of 5 MW/m3. Pebble fuels also permit radial zoning in annular cores and use of thorium or graphite pebble blankets to reduce neutron fluences to outer radial reflectors and increase total power production. Combined with high power conversion efficiency, compact low-pressure primary and containment systems, and unique safety characteristics including very large thermal margins (>500°C) to fuel damage during transients and accidents, salt-cooled pebble fuel cores offer the potential to meet the major goals of the Advanced Reactor Concepts Development program to provide electricity at lower cost than light water reactors with improved safety and system performance.This report presents the facility description, experimental results, and supporting simulation methods of the new X-Ray Pebble Recirculation Experiment (X-PREX), which is now operational and being used to collect data on the behavior of slow dense granular flows relevant to pebble bed reactor core designs. The X

  15. Millisecond autothermal catalytic reforming of carbohydrates for synthetic fuels by reactive flash volatilization

    NASA Astrophysics Data System (ADS)

    Dauenhauer, Paul Jakob

    Carbohydrates including glucose, cellulose, starch and polyols including glycerol, ethylene glycol and methanol produced in large quantities from biomass are considered as a carbon-based feedstock for high temperature catalytic reforming by catalytic partial oxidation. Autothermal catalytic partial oxidation of methanol, ethylene glycol, and glycerol with Rh and Pt-based catalysts with ceria on alumina foam supports at residence times less than ten milliseconds produced equilibrium selectivity to synthesis gas. The addition of steam at S/C>4 produced selectivity to H2 higher than 80% with little or no selectivity to minor products. In a new process referred to as 'reactive flash volatilization,' catalytic partial oxidation was combined with pyrolysis of biomass by directly impinging particles of cellulose, starch, polyethylene, soy oil, or Aspen (Populous Tremuloides) on an operating Rh-based reforming catalyst at 700-800°C. Solid particles endothermically pyrolyzed to volatile organic compounds which mixed with air and reformed on the catalyst exothermically generating heat to drive the overall process. Particles of ˜250 mum microcrystalline cellulose processed at the conditions of C/O=1.0 on a RhCe/gamma-Al2O3/alpha-Al 2O3 at a residence time of ˜70 milliseconds produced a gaseous effluent stream selecting for 50% H2 and 50% CO with no observable side products other than H2O and CO2, and <1% CH4. To obtain a more optimal synthesis gas stream, the reforming of ˜400 mum microcrystalline particles was examined over a fixed bed of RhCe/gamma-Al2O3/alpha-Al2O 3 spheres by varying the feed ratio of N2/O2, the temperature of the feed gas, the total particle feed rate, and the addition of steam permitting cellulose conversion with ˜75% fuel efficiency. Cellulose, sucrose, and glycerol particle conversion was examined with high-speed photography (1000 frames/second) revealing the formation of a liquid intermediate from cellulose permitting extremely high heat flux (

  16. Formation of tetragonal hydrogen tungsten bronze by reactive mechanical alloying

    SciTech Connect

    Urretavizcaya, G. Tonus, F.; Gaudin, E.; Bobet, J.-L.; Castro, F.J.

    2007-10-15

    Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying monoclinic tungsten (VI) oxide under hydrogen atmosphere. Two milling devices with different energy ranges were used. Regardless of the distinct reaction times, a similar phase evolution was observed with both apparatus. The characterization of the materials was performed by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. - Graphical abstract: Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying (RMA) monoclinic WO{sub 3} under H{sub 2} atmosphere. By using two milling devices with different energy ranges a similar phase evolution with distinct reaction times was observed. The materials were characterized by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. Display Omitted.

  17. Investigation of the Effect of Fixed Absorbers on the Reactivity of PWR Spent Nuclear Fuel for Burnup Credit

    SciTech Connect

    Wagner, John C.; Sanders, Charlotta E.

    2002-08-15

    The effect of fixed absorbers on the reactivity of pressurized water reactor (PWR) spent nuclear fuel (SNF) in support of burnup-credit criticality safety analyses is examined. A fuel assembly burned in conjunction with fixed absorbers may have a higher reactivity for a given burnup than an assembly that has not used fixed absorbers. As a result, guidance on burnup credit, issued by the U.S. Nuclear Regulatory Commission's Spent Fuel Project Office, recommends restricting the use of burnup credit to assemblies that have not used burnable absorbers. This recommendation eliminates a large portion of the currently discharged SNF from loading in burnup credit casks and thus severely limits the practical usefulness of burnup credit. Therefore, data are needed to support the extension of burnup credit to additional SNF. This research investigates the effect of various fixed absorbers, including integral burnable absorbers, burnable poison rods, control rods, and axial power shaping rods, on the reactivity of PWR SNF. Trends in reactivity with relevant parameters (e.g., initial fuel enrichment, burnup and absorber type, exposure, and design) are established, and anticipated reactivity effects are quantified. Where appropriate, recommendations are offered for addressing the reactivity effects of the fixed absorbers in burnup-credit safety analyses.

  18. Effect of fuel molecular structure on soot formation in gas turbine engines

    NASA Technical Reports Server (NTRS)

    Naegeli, D. W.; Moses, C. A.

    1980-01-01

    A high-pressure research combustor operating over a wide range of burner inlet conditions was used to determine the effects of fuel molecular structure on soot formation. Six test fuels with equal hydrogen content (12.8 percent) were blended to stress different molecular components and final boiling points. The fuels containing high concentrations (20 percent) of poly-cyclic aromatics and partially saturated polycyclic structures such as tetralin, produced more soot than would be expected from a hydrogen content correlation for typical petroleum based fuels. However, fuels containing naphthenes, such as decalin, agreed with the hydrogen content correlation. The contribution of polycylic aromatics to soot formation was equivalent to a reduction in fuel hydrogen content of about 1%. The fuel sensitivity to soot formation due to the polycyclic aromatic contribution decreased as burner inlet pressure and fuel/air ratio increased.

  19. Simulation of Supersonic Reactive Flow in Ramped Cavity Combustor with Fuel Injector

    NASA Astrophysics Data System (ADS)

    Ghiasi, Zia; Komperda, Jonathan; Li, Dongru; Mashayek, Farzad; Computational Multiphase Transport Laboratory Team

    2014-11-01

    Numerical simulation of supersonic reactive flows is emerging as an essential stage toward efficient design and development of scramjets. The flow inside the combustion chamber of scramjet is a prime example of multi-scale and multi-physics flow and is often accompanied by concurrent presence of shock waves and turbulence. Developing a robust numerical method for such simulations leads to numerous challenges due to the presence of complex geometries, shocks, turbulence and chemical reaction, which require massively parallel computation. In the present work we use the Discontinuous Spectral Element Method (DSEM) for high-fidelity simulation of reactive, supersonic and turbulent flows. The code features an entropy-based artificial viscosity method for capturing shock waves and uses implicit Large Eddy Simulation (LES) method for turbulence modeling. The turbulence-combustion interaction is captured using the Filtered Mass Density Function (FMDF) method. A supersonic reactive flow within a ramped cavity flame holder with round fuel injectors is simulated for hydrogen/air reaction, and the physics of the flow is studied.

  20. Formation and reactivity of vinylperoxyl radicals in aqueous solutions

    SciTech Connect

    Khaikin, G.I.; Neta, P.

    1995-03-30

    Vinyl, carboxyvinyl and dicarboxyvinyl radicals were produced in irradiated aqueous solutions from acetylene and acetylenecarboxylic and acetylenedicarboxylic acid by addition of H atom to the triple bond or by reaction with e{sub aq}{sup -}, followed by protonation. Vinyl and phenylvinyl radicals were produced by reductive dehalogenation of vinyl bromide and {beta}-bromostyrene with e{sub aq}{sup -}. All these vinyl radicals react rapidly with oxygen to produce the corresponding vinylperoxyl radicals. Vinylperoxyl radicals exhibit optical absorptions in the UV ({lambda}{sub max} 250-290 nm) and in the visible range. The peaks in the visible range were at 440 nm for unsubstituted vinylperoxyl radical, between 480 and 520 nm for carboxylated vinylperoxyl, depending on pH and number of carboxyl groups, and at 540 and 690 nm for (2-phenylvinyl)peroxyl. These vinylperoxyl radicals oxidize organic reductants such as 2,2`azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS), chlorpromazine, ascorbate, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) with rate constants between 4 x 10{sup 5} and 2 x 10{sup 9} L mol{sup -1} s{sup -1}, depending on the radical and the reductant. Vinylperoxyl radicals are more reactive than similarly substituted alkylperoxyl. 20 refs., 5 figs., 1 tab.

  1. Analyzing the impact of reactive transport on the repository performance of TRISO fuel

    NASA Astrophysics Data System (ADS)

    Schmidt, Gregory

    graphite surrounding the spent HTGR fuel will impact the release of aqueous uranium from the TRISO fuel. In order to answer this question, the sorption and partitioning behavior of uranium to graphite under a variety of conditions was investigated. Key systematic variables that were analyzed include solution pH, dissolved carbonate concentration, uranium metal concentration and ionic strength. The kinetics and desorption characteristics of uranium/graphite partitioning were studied as well. The graphite used in these experiments was also characterized by a variety of techniques and conclusions are drawn about the relevant surface chemistry of graphite. This data was then used to generate a model for the reactive transport of uranium in a graphite matrix. This model was implemented with the software code CXTFIT and validated through the use of column studies mirroring the predicted system.

  2. Formation Processes and Impacts of Reactive and Nonreactive Minerals in Permeable Reactive Barriers

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., changes in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction,...

  3. Formation of Reactive Br Species by Freezing in Solutions of NaBr-Metal-Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Kinjo, M.; Arakaki, T.

    2005-12-01

    The role of reactive halogen species (e.g. BrOH) in the destruction of stratospheric ozone is well known and largely understood. In recent years, it became clear that reactive Br species can also play a significant role in tropospheric ozone destruction, but sources of reactive Br species in the troposphere are not well understood. When an aqueous solution is frozen, solutes in the solution are excluded from the ice phase and the solutes are concentrated in the solution phase. Freezing processes cause red-ox reactions in the solution. We tried to understand the effects of freezing processes of solutions on formation of reactive Br species. Hydrogen peroxide (HOOH) and metallic ions were added to a mixing solution of NaBr and allyl alcohol (AA). If reactive Br species are formed, they react with AA, and free Br ion concentration decreases in the solution. When HOOH and Fe(III) or Cu(II) were added to the NaBr and AA solution and frozen, free Br ion concentration decreased. It is possible that OH radical formation from reaction between HOOH and Fe(II) or Cu(I) was induced by freezing processes and the OH radical probably oxidized Br ion to reactive Br species. Study of the effects of pH showed that decrease of Br ion concentration was the highest at pH = 4.0. Freezing processes could be an important source of reactive Br species in high altitude clouds and Polar Regions.

  4. PRD (power-reactivity-decrement) components of a homogeneous U10Zr-fueled 900 MWt LMR

    SciTech Connect

    Meneghetti, D.; Kucera, D.A.

    1988-01-01

    The linear and Doppler feedback components of the regional contributions of the power-reactivity-decrement (PRD) for a representative 900 MWt homogeneous U10Zr-fueled sodium-cooled reactor are calculated. The PRD is the reactivity required to bring the reactor from zero-power hot-critical condition to a given power level. These components are further separated into power dependent and power-to-flow dependent parts. The values are compared with corresponding quantities calculated for the Experimental Breeder Reactor II (EBR-II). The implications of these comparisons upon inherent safety characteristics of metal-fueled sodium-cooled reactors are discussed. The effects of fuel axial restraint on feedback, resulting from possible fuel-clad interactions due to burnup are also calculated. The possible enhancement of desirable feedbacks by use of appropriately designed subassembly-duct bowing feedback characteristics is estimated.

  5. 40 CFR 600.302-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Fuel economy label format requirements. 600.302-08 Section 600.302-08 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy...

  6. 40 CFR 600.310-12 - Fuel economy label format requirements-electric vehicles.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Fuel economy label format requirements-electric vehicles. 600.310-12 Section 600.310-12 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel...

  7. Environmental implications of iron fuel borne catalysts and their effects on diesel particulate formation and composition

    EPA Science Inventory

    Metal fuel borne catalysts can be used with diesel fuels to effectively reduce engine out particle mass emissions. Mixed with the fuel, the metals become incorporated as nanometer-scale occlusions with soot during its formation and are available to promote in-cylinder soot oxida...

  8. Effect of Fuel Variables on Carbon Formation in Turbojet-Engine Combustors

    NASA Technical Reports Server (NTRS)

    Jonash, Edmund R; Wear, Jerrold D; Cook, William P

    1958-01-01

    Report presents the results of an investigation of the effects of fuel properties and of a number of fuel additives on combustion-chamber carbon deposition and exhaust-gas smoke formation in a single tubular turbojet-engine combustor. Limited tests were conducted with a number of the fuels in several full-scale turbojet engines to verify single-combustor data.

  9. Formation and Reactivity of Organo-Functionalized Tin Selenide Clusters.

    PubMed

    Rinn, Niklas; Eußner, Jens P; Kaschuba, Willy; Xie, Xiulan; Dehnen, Stefanie

    2016-02-24

    Reactions of R(1) SnCl3 (R(1) =CMe2 CH2 C(O)Me) with (SiMe3 )2 Se yield a series of organo-functionalized tin selenide clusters, [(SnR(1) )2 SeCl4 ] (1), [(SnR(1) )2 Se2 Cl2 ] (2), [(SnR(1) )3 Se4 Cl] (3), and [(SnR(1) )4 Se6 ] (4), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3 SiCl. Furthermore, addition of hydrazines to the keto-functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2 (μ-R(3) )(μ-Se)Cl4 ] (5, R(3) =[CMe2 CH2 CMe(NH)]2 ), [(SnR(2) )3 Se4 Cl] (6, R(2) =CMe2 CH2 C(NNH2 )Me), [(SnR(4) )3 Se4 ][SnCl3 ] (7, R(4) =CMe2 CH2 C(NNHPh)Me), [(SnR(2) )4 Se6 ] (8), and [(SnR(4) )4 Se6 ] (9). Upon treatment of 4 with [Cu(PPh3 )3 Cl] and excess (SiMe3 )2 Se, the cluster fragments to form [(R(1) Sn)2 Se2 (CuPPh3 )2 Se2 ] (10), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry.

  10. A Study on Reactive Spray Deposition Technology Processing Parameters in the Context of Pt Nanoparticle Formation

    NASA Astrophysics Data System (ADS)

    Roller, Justin M.; Maric, Radenka

    2015-12-01

    Catalytic materials are complex systems in which achieving the desired properties (i.e., activity, selectivity and stability) depends on exploiting the many degrees of freedom in surface and bulk composition, geometry, and defects. Flame aerosol synthesis is a process for producing nanoparticles with ample processing parameter space to tune the desired properties. Flame dynamics inside the reactor are determined by the input process variables such as solubility of precursor in the fuel; solvent boiling point; reactant flow rate and concentration; flow rates of air, fuel and the carrier gas; and the burner geometry. In this study, the processing parameters for reactive spray deposition technology, a flame-based synthesis method, are systematically evaluated to understand the residence times, reactant mixing, and temperature profiles of flames used in the synthesis of Pt nanoparticles. This provides a framework for further study and modeling. The flame temperature and length are also studied as a function of O2 and fuel flow rates.

  11. Performance of Transuranic-Loaded Fully Ceramic Micro-Encapsulated Fuel in LWRs Final Report, Including Void Reactivity Evaluation

    SciTech Connect

    Michael A. Pope; R. Sonat Sen; Brian Boer; Abderrafi M. Ougouag; Gilles Youinou

    2011-09-01

    The current focus of the Deep Burn Project is on once-through burning of transuranics (TRU) in light-water reactors (LWRs). The fuel form is called Fully-Ceramic Micro-encapsulated (FCM) fuel, a concept that borrows the tri-isotropic (TRISO) fuel particle design from high-temperature reactor technology. In the Deep Burn LWR (DB-LWR) concept, these fuel particles are pressed into compacts using SiC matrix material and loaded into fuel pins for use in conventional LWRs. The TRU loading comes from the spent fuel of a conventional LWR after 5 years of cooling. Unit cell and assembly calculations have been performed using the DRAGON-4 code to assess the physics attributes of TRU-only FCM fuel in an LWR lattice. Depletion calculations assuming an infinite lattice condition were performed with calculations of various reactivity coefficients performed at each step. Unit cells and assemblies containing typical UO2 and mixed oxide (MOX) fuel were analyzed in the same way to provide a baseline against which to compare the TRU-only FCM fuel. Then, assembly calculations were performed evaluating the performance of heterogeneous arrangements of TRU-only FCM fuel pins along with UO2 pins.

  12. Aerobic granular sludge inoculated microbial fuel cells for enhanced epoxy reactive diluent wastewater treatment.

    PubMed

    Cheng, Kai; Hu, Jingping; Hou, Huijie; Liu, Bingchuan; Chen, Qin; Pan, Keliang; Pu, Wenhong; Yang, Jiakuan; Wu, Xu; Yang, Changzhu

    2017-04-01

    Microbial consortiums aggregated on the anode surface of microbial fuel cells (MFCs) are critical factors for electricity generation as well as biodegradation efficiencies of organic compounds. Here in this study, aerobic granular sludge (AGS) was assembled on the surface of the MFC anode to form an AGS-MFC system with superior performance on epoxy reactive diluent (ERD) wastewater treatment. AGS-MFCs successfully shortened the startup time from 13d to 7d compared to the ones inoculated with domestic wastewater. Enhanced toxicity tolerance as well as higher COD removal (77.8% vs. 63.6%) were achieved. The higher ERD wastewater treatment efficiency of AGS-MFC is possibly attributed to the diverse microbial population on MFC biofilm, as well as the synergic degradation of contaminants by both the MFC anode biofilm and AGS granules.

  13. Power and power-to-flow reactivity transfer functions in EBR-II (Experimental Breeder Reactor II) fuel

    SciTech Connect

    Grimm, K.N.; Meneghetti, D. )

    1989-11-01

    Reactivity transfer functions are important in determining the reactivity history during a power transient. Overall nodal transfer functions have been calculated for different subassembly types in the Experimental Breeder Reactor II (EBR-II). Steady-state calculations for temperature changes and, hence, reactivities for power changes have been separated into power and power-to-flow-dependent terms. Axial nodal transfer functions separated into power and power-to-flow-dependent components are reported in this paper for a typical EBR-II fuel pin. This provides an improved understanding of the time dependence of these components in transient situations.

  14. 76 FR 65544 - Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-21

    ... issuance of the guide (74 FR 36780). The comment period closed on September 21, 2009. The staff's responses... COMMISSION Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities... Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities.'' This...

  15. Fuel Structure and Pressure Effects on the Formation of Soot Particles in Diffusion Flames

    DTIC Science & Technology

    1990-05-01

    higher values of the pressure power dependence appear to be related to fuel structure effects , the direct nature of which remains to be understood...61102F 2308 A2 11. TITLE (Include Security Classification) "Fuel Structure and Pressure Effects on the Formation of Soot Particlesin Diffusion Flames...block number) Studies emphasizing the effects of fuel concentration and operating pressure on the formation of soot particles have been conducted in a

  16. Formation and reactivity of pyridylperoxyl radicals in solution

    SciTech Connect

    Alfassi, Z.B.; Khaikin, G.I.; Neta, P.

    1995-03-30

    2-Pyridyl radicals were produced by the reaction of 2-chloro- or 2-bromopyridine with solvated electrons (k approximately 10{sup 10} L mol{sup -1} s{sup -1}) and reacted rapidly with oxygen (k = 2.2 x 10{sup 9} L mol{sup -1} s{sup -1}) to produce the 2-pyridylperoxyl radical. This radical exhibits optical absorption in the visible range, with {lambda}{sub max} at 440 nm. 2-Pyridylperoxyl radical is a fairly strong oxidant, which reacts with 2,2`-azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation as a function of substrate concentration, vary between 2 x 10{sup 6} and 2 x 10{sup 9} L mol{sup -1} s{sup -1} in various mixtures. For each substrate, a good correlation was found between log k and the cohesive pressure of the solvent or solvent mixture, as found before for CCI{sub 3}O{sub 2} radical reactions in nearly neat solvents. 3-Bromo, 3-chloro- and 4-chloropyridine also reacted rapidly with solvated electrons, but their radical anions underwent protonation on the nitrogen in competition with the dehalogenation process. Therefore, no pyridylperoxyl radicals were formed from these species in aqueous solutions and only partial yield was found in neat methanol. 20 refs., 4 figs., 1 tab.

  17. Involvement of Cytochrome P450 in Reactive Oxygen Species Formation and Cancer.

    PubMed

    Hrycay, Eugene G; Bandiera, Stelvio M

    2015-01-01

    This review examines the involvement of cytochrome P450 (CYP) enzymes in the formation of reactive oxygen species in biological systems and discusses the possible involvement of reactive oxygen species and CYP enzymes in cancer. Reactive oxygen species are formed in biological systems as byproducts of the reduction of molecular oxygen and include the superoxide radical anion (∙O2-), hydrogen peroxide (H2O2), hydroxyl radical (∙OH), hydroperoxyl radical (HOO∙), singlet oxygen ((1)O2), and peroxyl radical (ROO∙). Two endogenous sources of reactive oxygen species are the mammalian CYP-dependent microsomal electron transport system and the mitochondrial electron transport chain. CYP enzymes catalyze the oxygenation of an organic substrate and the simultaneous reduction of molecular oxygen. If the transfer of oxygen to a substrate is not tightly controlled, uncoupling occurs and leads to the formation of reactive oxygen species. Reactive oxygen species are capable of causing oxidative damage to cellular membranes and macromolecules that can lead to the development of human diseases such as cancer. In normal cells, intracellular levels of reactive oxygen species are maintained in balance with intracellular biochemical antioxidants to prevent cellular damage. Oxidative stress occurs when this critical balance is disrupted. Topics covered in this review include the role of reactive oxygen species in intracellular cell signaling and the relationship between CYP enzymes and cancer. Outlines of CYP expression in neoplastic tissues, CYP enzyme polymorphism and cancer risk, CYP enzymes in cancer therapy and the metabolic activation of chemical procarcinogens by CYP enzymes are also provided.

  18. Formation of thin walled ceramic solid oxide fuel cells

    DOEpatents

    Claar, Terry D.; Busch, Donald E.; Picciolo, John J.

    1989-01-01

    To reduce thermal stress and improve bonding in a high temperature monolithic solid oxide fuel cell (SOFC), intermediate layers are provided between the SOFC's electrodes and electrolyte which are of different compositions. The intermediate layers are comprised of a blend of some of the materials used in the electrode and electrolyte compositions. Particle size is controlled to reduce problems involving differential shrinkage rates of the various layers when the entire structure is fired at a single temperature, while pore formers are provided in the electrolyte layers to be removed during firing for the formation of desired pores in the electrode layers. Each layer includes a binder in the form of a thermosetting acrylic which during initial processing is cured to provide a self-supporting structure with the ceramic components in the green state. A self-supporting corrugated structure is thus formed prior to firing, which the organic components of the binder and plasticizer removed during firing to provide a high strength, high temperature resistant ceramic structure of low weight and density.

  19. The HIF-1 inhibitor YC-1 decreases reactive astrocyte formation in a rodent ischemia model

    PubMed Central

    Na, Jong-In; Na, Joo-Young; Choi, Woo-Young; Lee, Min-Cheol; Park, Man-Seok; Choi, Kang-Ho; Lee, Jeong-Kil; Kim, Kyung-Tae; Park, Jong-Tae; Kim, Hyung-Seok

    2015-01-01

    Astrocytes become reactive after central nervous system injury, re-expressing glial fibrillary acidic protein (GFAP), vascular endothelial growth factor (VEGF), and nestin. Hypoxia-inducible transcription factor alpha (HIF-1α) is an important transcription factor for several genes including the VEGF and nestin genes, the expression of which generate reactive astrocytes and cause gliosis after cerebral ischemia. To evaluate the role of HIF-1α in reactive astrocyte formation, we applied the potent HIF-1α inhibitor YC-1 to a focal cerebral ischemia model and analyzed the expression of HIF-1α, VEGF, nestin, and GFAP. Quantitative real-time reverse transcription polymerase chain reaction and western blot analyses demonstrated that the expression of HIF-1α and its downstream genes (VEGF and nestin) were markedly attenuated in the YC-1-treated group versus the control group (HIF-1α, VEGF: p < 0.01; nestin: p < 0.05). GFAP expression was also effectively inhibited in the YC-1-treated group (p < 0.05). Immunohistochemical evaluations showed that GFAP-positive (GFAP+) cells in the YC-1-treated group were sparse in the peri-infarct area, while an immunofluorescence assay revealed that the number of VEGF+/GFAP+ and nestin+/GFAP+ reactive astrocytes were decreased in the YC-1-treated group (p < 0.05). These results demonstrate that HIF-1α suppression decreases the formation of reactive astrocytes and gliosis that occur following focal ischemia. PMID:26064442

  20. 40 CFR 600.308-12 - Fuel economy label format requirements-plug-in hybrid electric vehicles.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Fuel economy label format requirements... PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Labeling § 600.308-12 Fuel economy label format requirements—plug-in hybrid...

  1. Oxidation and formation of deposit precursors in hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Buttrill, S. E., Jr.; Mayo, F. R.; Lan, B.; St.john, G. A.; Dulin, D.

    1982-01-01

    A practical fuel, home heating oil no. 2 (Fuel C), and the pure hydrocarbon, n-dodecane, were subjected to mild oxidation at 130 C and the resulting oxygenated reaction products, deposit precursors, were analyzed using field ionization mass spectrometry. Results for fuel C indicated that, as oxidation was initially extended, certain oxygenated reaction products of increasing molecular weights in the form of monomers, dimers and some trimers were produced. Further oxidation time increase resulted in further increase in monomers but a marked decrease in dimers and trimers. This suggests that these larger molecular weight products have proceeded to form deposit and separated from the fuel mixture. Results for a dodecane indicated that yields for dimers and trimers were very low. Dimers were produced as a result of interaction between oxygenated products with each other rather than with another fuel molecule. This occurred even though fuel molecule concentration was 50 times, or more greater than that for these oxygenated reaction products.

  2. Formation of iron nanoparticles and increase in iron reactivity in mineral dust during simulated cloud processing.

    PubMed

    Shi, Zongbo; Krom, Michael D; Bonneville, Steeve; Baker, Alex R; Jickells, Timothy D; Benning, Liane G

    2009-09-01

    The formation of iron (Fe) nanoperticles and increase in Fe reactivity in mineral dust during simulated cloud processing was investigated using high-resolution microscopy and chemical extraction methods. Cloud processing of dust was experimentally simulated via an alternation of acidic (pH 2) and circumneutral conditions (pH 5-6) over periods of 24 h each on presieved (<20 microm) Saharan soil and goethite suspensions. Microscopic analyses of the processed soil and goethite samples reveal the neo-formation of Fe-rich nanoparticle aggregates, which were not found initially. Similar Fe-rich nanoparticles were also observed in wet-deposited Saharen dusts from the western Mediterranean but not in dry-deposited dust from the eastern Mediterranean. Sequential Fe extraction of the soil samples indicated an increase in the proportion of chemically reactive Fe extractable by an ascorbate solution after simulated cloud processing. In addition, the sequential extractions on the Mediterranean dust samples revealed a higher content of reactive Fe in the wet-deposited dust compared to that of the dry-deposited dust These results suggestthat large variations of pH commonly reported in aerosol and cloud waters can trigger neo-formation of nanosize Fe particles and an increase in Fe reactivity in the dust

  3. Incremental Reactivity Effects on Secondary Organic Aerosol Formation in Urban Atmospheres with and without Biogenic Influence

    NASA Astrophysics Data System (ADS)

    Kacarab, Mary; Li, Lijie; Carter, William P. L.; Cocker, David R., III

    2016-04-01

    Two different surrogate mixtures of anthropogenic and biogenic volatile organic compounds (VOCs) were developed to study secondary organic aerosol (SOA) formation at atmospheric reactivities similar to urban regions with varying biogenic influence levels. Environmental chamber simulations were designed to enable the study of the incremental aerosol formation from select anthropogenic (m-Xylene, 1,2,4-Trimethylbenzene, and 1-Methylnaphthalene) and biogenic (α-pinene) precursors under the chemical reactivity set by the two different surrogate mixtures. The surrogate reactive organic gas (ROG) mixtures were based on that used to develop the maximum incremental reactivity (MIR) factors for evaluation of O3 forming potential. Multiple incremental aerosol formation experiments were performed in the University of California Riverside (UCR) College of Engineering Center for Environmental Research and Technology (CE-CERT) dual 90m3 environmental chambers. Incremental aerosol yields were determined for each of the VOCs studied and compared to yields found from single precursor studies. Aerosol physical properties of density, volatility, and hygroscopicity were monitored throughout experiments. Bulk elemental chemical composition from high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) data will also be presented. Incremental yields and SOA chemical and physical characteristics will be compared with data from previous single VOC studies conducted for these aerosol precursors following traditional VOC/NOx chamber experiments. Evaluation of the incremental effects of VOCs on SOA formation and properties are paramount in evaluating how to best extrapolate environmental chamber observations to the ambient atmosphere and provides useful insights into current SOA formation models. Further, the comparison of incremental SOA from VOCs in varying surrogate urban atmospheres (with and without strong biogenic influence) allows for a unique perspective on the impacts

  4. Elevated Cytosolic Na+ Increases Mitochondrial Formation of Reactive Oxygen Species in Failing Cardiac Myocytes

    PubMed Central

    Kohlhaas, Michael; Liu, Ting; Knopp, Andreas; Zeller, Tanja; Ong, Mei Fang; Böhm, Michael; O'Rourke, Brian; Maack, Christoph

    2010-01-01

    Background —Oxidative stress is causally linked to the progression of heart failure, and mitochondria are critical sources of reactive oxygen species in failing myocardium. We previously observed that in heart failure, elevated cytosolic Na+ ([Na+]i) reduces mitochondrial Ca2+ ([Ca2+]m) by accelerating Ca2+ efflux via the mitochondrial Na+/Ca2+ exchanger. Because the regeneration of antioxidative enzymes requires NADPH, which is indirectly regenerated by the Krebs cycle, and Krebs cycle dehydrogenases are activated by [Ca2+]m, we speculated that in failing myocytes, elevated [Na+]i promotes oxidative stress. Methods and Results —We used a patch-clamp–based approach to simultaneously monitor cytosolic and mitochondrial Ca2+ and, alternatively, mitochondrial H2O2 together with NAD(P)H in guinea pig cardiac myocytes. Cells were depolarized in a voltage-clamp mode (3 Hz), and a transition of workload was induced by β-adrenergic stimulation. During this transition, NAD(P)H initially oxidized but recovered when [Ca2+]m increased. The transient oxidation of NAD(P)H was closely associated with an increase in mitochondrial H2O2 formation. This reactive oxygen species formation was potentiated when mitochondrial Ca2+ uptake was blocked (by Ru360) or Ca2+ efflux was accelerated (by elevation of [Na+]i). In failing myocytes, H2O2 formation was increased, which was prevented by reducing mitochondrial Ca2+ efflux via the mitochondrial Na+/Ca2+ exchanger. Conclusions —Besides matching energy supply and demand, mitochondrial Ca2+ uptake critically regulates mitochondrial reactive oxygen species production. In heart failure, elevated [Na+]i promotes reactive oxygen species formation by reducing mitochondrial Ca2+ uptake. This novel mechanism, by which defects in ion homeostasis induce oxidative stress, represents a potential drug target to reduce reactive oxygen species production in the failing heart. PMID:20351235

  5. Fuel Efficient Strategies for Reducing Contrail Formations in United States Air Space

    NASA Technical Reports Server (NTRS)

    Sridhar, Banavar; Chen, Neil Y.; Ng, Hok K.

    2010-01-01

    This paper describes a class of strategies for reducing persistent contrail formation in the United States airspace. The primary objective is to minimize potential contrail formation regions by altering the aircraft's cruising altitude in a fuel-efficient way. The results show that the contrail formations can be reduced significantly without extra fuel consumption and without adversely affecting congestion in the airspace. The contrail formations can be further reduced by using extra fuel. For the day tested, the maximal reduction strategy has a 53% contrail reduction rate. The most fuel-efficient strategy has an 8% reduction rate with 2.86% less fuel-burnt compared to the maximal reduction strategy. Using a cost function which penalizes extra fuel consumed while maximizing the amount of contrail reduction provides a flexible way to trade off between contrail reduction and fuel consumption. It can achieve a 35% contrail reduction rate with only 0.23% extra fuel consumption. The proposed fuel-efficient contrail reduction strategy provides a solution to reduce aviation-induced environmental impact on a daily basis.

  6. Effects of fracture reactivation and diagenesis on fracture network evolution: Cambrian Eriboll Formation, NW Scotland

    NASA Astrophysics Data System (ADS)

    Hooker, J. N.; Eichhubl, P.; Xu, G.; Ahn, H.; Fall, A.; Hargrove, P.; Laubach, S.; Ukar, E.

    2011-12-01

    The Cambrian Eriboll Formation quartzarenites contain abundant fractures with varying degrees of quartz cement infill. Fractures exist that are entirely sealed; are locally sealed by bridging cements but preserve pore space among bridges; are mostly open but lined with veneers of cement; or are devoid of cement. Fracture propagation in the Eriboll Formation is highly sensitive to the presence of pre-existing fractures. Fracture reactivation occurs in opening mode as individual fractures repeatedly open and are filled or bridged by syn-kinematic cements. As well, reactivation occurs in shear as opening of one fracture orientation coincides with shear displacement along pre-existing fractures of different orientations. The tendency for pre-existing fractures to slip varies in part by the extent of cement infill, yet we observe shear and opening-mode reactivation even among sealed fractures. Paleotemperature analysis of fluid inclusions within fracture cements suggests some fractures now in outcrop formed deep in the subsurface. Fractures within the Eriboll Formation may therefore affect later fracture propagation throughout geologic time. With progressive strain, fault zones develop within fracture networks by a sequence of opening-mode fracture formation, fracture reactivation and linkage, fragmentation, cataclasis, and the formation of slip surfaces. Cataclasite within fault zones is commonly more thoroughly cemented than fractures in the damage zone or outside the fault zone. This variance of cement abundance is likely the result of (1) continued exposure of freshly broken quartz surfaces within cataclasite, promoting quartz precipitation, and (2) possibly more interconnected pathways for mass transfer within the fault zone. Enhanced cementation of cataclasite results in strengthening or diagenetic strain hardening of the evolving fault zone. Further slip is accommodated by shear localization along discrete slip surfaces. With further linkage of fault segments

  7. [Cytochromes P450 and formation of reactive metabolites. Role in hepatotoxicity of drugs].

    PubMed

    Pessayre, D

    1993-01-01

    During the millennia of evolution, animals have been subjected to a relentless biological warfare mounted by the plants that they ingested. By duplication of an ancestral gene, divergent evolution of these 2 genes, and so forth, surviving animals have been endowed with multiple cytochromes P450s which can metabolize (and thus eliminate) a multitude of environmental liposoluble xenobiotics. A disadvantage of this system (fortunately limited by the concomitant installation of several protective systems) is that cytochrome P450 transforms some of these xenobiotics into chemically reactive metabolites. These free radicals or electrophilic metabolites attack tissue constituents, and may lead to mutation, cancer or tissue necrosis. Tissue necrosis affect mainly the liver, whose content in cytochrome P450 is particularly high. Indeed, reactive metabolites are usually extremely unstable, and react mainly in situ, in the same organ that forms them. When the formation of reactive metabolites is extensive, protective mechanisms are overwhelmed, extensive alterations of diverse hepatic constituents occur, and toxic hepatitis ensues. When the formation of reactive metabolites is moderate, severe toxic lesions do not occur. However, the covalent binding of reactive metabolites to hepatic proteins modifies the self of the subject. In some subjects, the presence of this modified self triggers immunization, and leads to immunoallergic hepatitis. The immune response may be directed either against protein (or peptide) epitopes modified by the presence of a reactive metabolite (reaction against modified self) and/or against normal, unmodified, epitopes of proteins (autoimmune reaction against the self, triggered by the modified self). Both metabolic factors, and the HLA phenotype, appear to modulate the likelihood of immunization.

  8. A Study of Pollutant Formation from the Lean Premixed Combustion of Gaseous Fuel Alternatives to Natural Gas

    NASA Astrophysics Data System (ADS)

    Fackler, Keith Boyd, Jr.

    emissions decrease with increasing H2 fuel fraction for combustion of CH4/H2 blends. This appears to be caused by a reduction in the amount of NO made by the prompt pathway involving the reaction of N2 with hydrocarbon radicals as the CH4 is replaced by H2. 2.) For category 2 (the process and refinery blend) and category 5 (the LNG, shale, and associated gases), NOx emissions increase with the addition of C2 and C3 hydrocarbons. This could be due to an increased production of free radicals resulting from increasing CO production when higher molecular weight hydrocarbons are broken down. 3.) For category 3 (the O2 blown gasified coal/petcoke), NOx emissions increase with increasing CO fuel fraction. The reason for this is attributed to CO producing more radicals per unit heat release than H2. When CO replaces H2, an increase in NOx emissions is seen due to an increase in the productivity of the N2O, NNH, and Zeldovich pathways. 4.) For category 4 (the landfill gas) the addition of diluents such as CO2 and N2 at constant air flow produces more NOx per kg of CH4 consumed, and N2 is more effective than CO 2 in increasing the NOx emission index. The increase in emission index appears to be due to an enhancement of the prompt NOx pathway as the diluents are added and the mixture moves towards stoichiometric. In addition, the presence of CO2 as a diluent catalyzes the loss of flame radicals, leading to less NOx formation than when an equivalent amount of N2 is used as a diluent. For a selected set of fuels, detailed spacial reactor probing is carried out. At the nominal temperature and residence time, the experimental results show the following trends for flame structure as a function of fuel type: 1.) Pure H2 is far more reactive in comparison to CH4 and all other pure alkane fuels. This results in relatively flat NO x and temperature profiles; whereas, the alkane fuels drop in both temperature and NOx production in the jet, where more fresh reactor feed gases are present. 2

  9. Examination of Mechanisms and Fuel-Molecular Effects on Soot Formation.

    DTIC Science & Technology

    1988-02-13

    11 TABLE V - REACTIONS AND RATE COEFFICIENTS FOR STEPS LEADING TO FORMATION OF AROMATIC RING .... .............. . 12 S TABLE...VI REACTIONS LEADING TO FORMATION OF POLYCYCLIC HYDROCARBONS ....... ..................... . 13 -V; R88-957047 Examination of Mechanisms and Fuel...corporate-sponsorship to facilitate interpreting data from CHEMKIN and CHEMSEN. Plots of 1. Species concentrations 2. Reaction contribution to the formation

  10. Reactivation of chromosomally integrated human herpesvirus-6 by telomeric circle formation.

    PubMed

    Prusty, Bhupesh K; Krohne, George; Rudel, Thomas

    2013-01-01

    More than 95% of the human population is infected with human herpesvirus-6 (HHV-6) during early childhood and maintains latent HHV-6 genomes either in an extra-chromosomal form or as a chromosomally integrated HHV-6 (ciHHV-6). In addition, approximately 1% of humans are born with an inheritable form of ciHHV-6 integrated into the telomeres of chromosomes. Immunosuppression and stress conditions can reactivate latent HHV-6 replication, which is associated with clinical complications and even death. We have previously shown that Chlamydia trachomatis infection reactivates ciHHV-6 and induces the formation of extra-chromosomal viral DNA in ciHHV-6 cells. Here, we propose a model and provide experimental evidence for the mechanism of ciHHV-6 reactivation. Infection with Chlamydia induced a transient shortening of telomeric ends, which subsequently led to increased telomeric circle (t-circle) formation and incomplete reconstitution of circular viral genomes containing single viral direct repeat (DR). Correspondingly, short t-circles containing parts of the HHV-6 DR were detected in cells from individuals with genetically inherited ciHHV-6. Furthermore, telomere shortening induced in the absence of Chlamydia infection also caused circularization of ciHHV-6, supporting a t-circle based mechanism for ciHHV-6 reactivation.

  11. A Statistical Approach to Predict the Failure Enthalpy and Reliability of Irradiated PWR Fuel Rods During Reactivity-Initiated Accidents

    SciTech Connect

    Nam, Cheol; Jeong, Yong-Hwan; Jung, Youn-Ho

    2001-11-15

    During the last decade, the failure behavior of high-burnup fuel rods under a reactivity-initiated accident (RIA) condition has been a serious concern since fuel rod failures at low enthalpy have been observed. This has resulted in the reassessment of existing licensing criteria and failure-mode study. To address the issue, a statistics-based methodology is suggested to predict failure probability of irradiated fuel rods under an RIA. Based on RIA simulation results in the literature, a failure enthalpy correlation for an irradiated fuel rod is constructed as a function of oxide thickness, fuel burnup, and pulse width. Using the failure enthalpy correlation, a new concept of ''equivalent enthalpy'' is introduced to reflect the effects of the three primary factors as well as peak fuel enthalpy into a single damage parameter. Moreover, the failure distribution function with equivalent enthalpy is derived, applying a two-parameter Weibull statistical model. Finally, the sensitivity analysis is carried out to estimate the effects of burnup, corrosion, peak fuel enthalpy, pulse width, and cladding materials used.

  12. Mechanism of carboxylic acid photooxidation in atmospheric aqueous phase: Formation, fate and reactivity

    NASA Astrophysics Data System (ADS)

    Charbouillot, Tiffany; Gorini, Sophie; Voyard, Guillaume; Parazols, Marius; Brigante, Marcello; Deguillaume, Laurent; Delort, Anne-Marie; Mailhot, Gilles

    2012-09-01

    In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals (rad OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward rad OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination. The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions.

  13. Fuel-optimal low-thrust formation reconfiguration via Radau pseudospectral method

    NASA Astrophysics Data System (ADS)

    Li, Jing

    2016-07-01

    This paper investigates fuel-optimal low-thrust formation reconfiguration near circular orbit. Based on the Clohessy-Wiltshire equations, first-order necessary optimality conditions are derived from the Pontryagin's maximum principle. The fuel-optimal impulsive solution is utilized to divide the low-thrust trajectory into thrust and coast arcs. By introducing the switching times as optimization variables, the fuel-optimal low-thrust formation reconfiguration is posed as a nonlinear programming problem (NLP) via direct transcription using multiple-phase Radau pseudospectral method (RPM), which is then solved by a sparse nonlinear optimization software SNOPT. To facilitate optimality verification and, if necessary, further refinement of the optimized solution of the NLP, formulas for mass costate estimation and initial costates scaling are presented. Numerical examples are given to show the application of the proposed optimization method. To fix the problem, generic fuel-optimal low-thrust formation reconfiguration can be simplified as reconfiguration without any initial and terminal coast arcs, whose optimal solutions can be efficiently obtained from the multiple-phase RPM at the cost of a slight fuel increment. Finally, influence of the specific impulse and maximum thrust magnitude on the fuel-optimal low-thrust formation reconfiguration is analyzed. Numerical results shown the links and differences between the fuel-optimal impulsive and low-thrust solutions.

  14. JAEA Studies on High Burnup Fuel Behaviors during Reactivity-Initiated Accident and Loss-of-Coolant Accident

    SciTech Connect

    Fuketa, Toyoshi; Sugiyama, Tomoyuki; Nagase, Fumihisa; Suzuki, Motoe

    2007-07-01

    The objectives of fuel safety research program at Japan Atomic Energy Agency (JAEA) are; to evaluate adequacy of present safety criteria and safety margins; to provide a database for future regulation on higher burnup UO{sub 2} and MOX fuels, new cladding and pellets; and to provide reasonably mechanistic computer codes for regulatory application. The JAEA program is comprised of reactivity-initiated accident (RIA) studies including pulse-irradiation experiments in the NSRR and cladding mechanical tests, loss-of-coolant accident (LOCA) tests including integral thermal shock test and oxidation rate measurement, development and verification of computer codes FEMAXI-6 and RANNS, and so on. In addition to an overview of the fuel safety research at JAEA, most recent progresses in the RIA and LOCA tests programs and the codes development are described and discussed in the paper. (authors)

  15. A high fuel utilizing solid oxide fuel cell cycle with regard to the formation of nickel oxide and power density

    NASA Astrophysics Data System (ADS)

    Nehter, Pedro

    Within this study a novel high fuel utilizing (High-uf) SOFC system is presented with special focus on the formation of nickel oxide, system efficiency and the required cell area at a fixed system performance of 1 MW. Within the High-uf SOFC cycle, a second SOFC stack is used to utilize a further part of the residual hydrogen of the first SOFC stack. This could be feasible by using an anode gas condenser, which is implemented between the first and the second stack. This reduces the water fraction of the anode gas and thereby the tendency of nickel oxide formation in case of a further fuel utilization. Thus, a higher total fuel utilization can be reached with the second SOFC stack. With the High-uf SOFC cycle, the system efficiency is increased by 7%-points compared to the simple atmospheric SOFC cycle. Furthermore, the average cell voltage and the fuel utilization are varied to carry out a first optimization of the stack's power density. The results of this optimization have shown that the required cell area of the simple SOFC cycle can be slightly reduced by decreasing the fuel utilization, whereas the High-uf SOFC cycle shows an opposite effect. Here, the required cell area can be reduced at constant voltages by increasing the fuel utilization. Thus, higher system efficiencies could be reached with the High-uf SOFC cycle by using the same cell area as the simple SOFC cycle and at the same tendency of nickel oxide formation. A second condenser behind the second SOFC stack could be used to increase the carbon dioxide mass fraction up to 92%. This could be interesting for CO 2-sequestring applications as well.

  16. In situ formation of magnetite reactive barriers in soil for waste stabilization

    DOEpatents

    Moore, Robert C.

    2003-01-01

    Reactive barriers containing magnetite and methods for making magnetite reactive barriers in situ in soil for sequestering soil contaminants including actinides and heavy metals, organic materials, iodine and technetium are disclosed. According to one embodiment, a two-step reagent introduction into soil takes place. In the first step, free oxygen is removed from the soil by separately injecting into the soil aqueous solutions of iron (II) salt, for example FeCl.sub.2, and base, for example NaOH or NH.sub.3 in about a 1:1 volume ratio. Then, in the second step, similar reagents are injected a second time (however, according to about a 1:2 volume ratio, iron to salt) to form magnetite. The magnetite formation is facilitated, in part, due to slow intrusion of oxygen into the soil from the surface. The invention techniques are suited to injection of reagents into soil in proximity to a contamination plume or source allowing in situ formation of the reactive barrier at the location of waste or hazardous material. Mixing of reagents to form. precipitate is mediated and enhanced through movement of reagents in soil as a result of phenomena including capillary action, movement of groundwater, soil washing and reagent injection pressure.

  17. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    DOE PAGES

    Wang, Jun; McEntee, Monica; Tang, Wenjie; ...

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

  18. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    SciTech Connect

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.

  19. Inhibitors of biofilm formation by fuel ethanol contaminants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Industrial fuel ethanol production suffers from chronic and acute infections that reduce yields and cause “stuck fermentations” that result in costly shutdowns. Lactic acid bacteria, particularly Lactobacillus sp., are recognized as major contaminants. In previous studies, we observed that certain...

  20. Chemical reactivity and skin sensitization potential for benzaldehydes: can Schiff base formation explain everything?

    PubMed

    Natsch, Andreas; Gfeller, Hans; Haupt, Tina; Brunner, Gerhard

    2012-10-15

    Skin sensitizers chemically modify skin proteins rendering them immunogenic. Sensitizing chemicals have been divided into applicability domains according to their suspected reaction mechanism. The widely accepted Schiff base applicability domain covers aldehydes and ketones, and detailed structure-activity-modeling for this chemical group was presented. While Schiff base formation is the obvious reaction pathway for these chemicals, the in silico work was followed up by limited experimental work. It remains unclear whether hydrolytically labile Schiff bases can form sufficiently stable epitopes to trigger an immune response in the living organism with an excess of water being present. Here, we performed experimental studies on benzaldehydes of highly differing skin sensitization potential. Schiff base formation toward butylamine was evaluated in acetonitrile, and a detailed SAR study is presented. o-Hydroxybenzaldehydes such as salicylaldehyde and the oakmoss allergens atranol and chloratranol have a high propensity to form Schiff bases. The reactivity is highly reduced in p-hydroxy benzaldehydes such as the nonsensitizing vanillin with an intermediate reactivity for p-alkyl and p-methoxy-benzaldehydes. The work was followed up under more physiological conditions in the peptide reactivity assay with a lysine-containing heptapeptide. Under these conditions, Schiff base formation was only observable for the strong sensitizers atranol and chloratranol and for salicylaldehyde. Trapping experiments with NaBH₃CN showed that Schiff base formation occurred under these conditions also for some less sensitizing aldehydes, but the reaction is not favored in the absence of in situ reduction. Surprisingly, the Schiff bases of some weaker sensitizers apparently may react further to form stable peptide adducts. These were identified as the amides between the lysine residues and the corresponding acids. Adduct formation was paralleled by oxidative deamination of the parent

  1. Liquid phase products and solid deposit formation from thermally stressed model jet fuels

    NASA Technical Reports Server (NTRS)

    Kim, W. S.; Bittker, D. A.

    1984-01-01

    The relationship between solid deposit formation and liquid degradation product concentration was studied for the high temperature (400 C) stressing of three hydrocarbon model fuels. A Jet Fuel Thermal Oxidation Tester was used to simulate actual engine fuel system conditions. The effects of fuel type, dissolved oxygen concentration, and hot surface contact time (reaction time) were studied. Effects of reaction time and removal of dissolved oxygen on deposit formation were found to be different for n-dodecane and for 2-ethylnaphthalene. When ten percent tetralin is added to n-dodecane to give a simpler model of an actual jet fuel, the tetralin inhibits both the deposit formation and the degradation of n-dodecane. For 2-ethylnaphthalene primary product analyses indicate a possible self-inhibition at long reaction times of the secondary reactions which form the deposit precursors. The mechanism of the primary breakdown of these fuels is suggested and the primary products which participate in these precursor-forming reactions are identified. Some implications of the results to the thermal degradation of real jet fuels are given.

  2. Extracellular ultrathin fibers sensitive to intracellular reactive oxygen species: Formation of intercellular membrane bridges

    SciTech Connect

    Jung, Se-Hui; Park, Jin-Young; Joo, Jung-Hoon; Kim, Young-Myeong; Ha, Kwon-Soo

    2011-07-15

    Membrane bridges are key cellular structures involved in intercellular communication; however, dynamics for their formation are not well understood. We demonstrated the formation and regulation of novel extracellular ultrathin fibers in NIH3T3 cells using confocal and atomic force microscopy. At adjacent regions of neighboring cells, phorbol 12-myristate 13-acetate (PMA) and glucose oxidase induced ultrathin fiber formation, which was prevented by Trolox, a reactive oxygen species (ROS) scavenger. The height of ROS-sensitive ultrathin fibers ranged from 2 to 4 nm. PMA-induced formation of ultrathin fibers was inhibited by cytochalasin D, but not by Taxol or colchicine, indicating that ultrathin fibers mainly comprise microfilaments. PMA-induced ultrathin fibers underwent dynamic structural changes, resulting in formation of intercellular membrane bridges. Thus, these fibers are formed by a mechanism(s) involving ROS and involved in formation of intercellular membrane bridges. Furthermore, ultrastructural imaging of ultrathin fibers may contribute to understanding the diverse mechanisms of cell-to-cell communication and the intercellular transfer of biomolecules, including proteins and cell organelles.

  3. Exploiting Formation Flying for Fuel Saving Supersonic Oblique Wing Aircraft

    DTIC Science & Technology

    2007-07-01

    examples of CFF Wind Tunnel work carried out in support of flight tests on the F/A-18. Fig.1.4 refers to CFF work on “ICE” models. Note the possibility of...of subsonic- transonic wings in formation and then re-designed them to eliminate the induced roll / pitch effects. A number of flight formations

  4. An Empirical Approach to Bounding the Axial Reactivity Effects of PWR Spent Nuclear Fuel

    SciTech Connect

    P. M. O'Leary; J. M. Scaglione

    2001-04-04

    One of the significant issues yet to be resolved for using burnup credit (BUC) for spent nuclear fuel (SNF) is establishing a set of depletion parameters that produce an adequately conservative representation of the fuel's isotopic inventory. Depletion parameters (such as local power, fuel temperature, moderator temperature, burnable poison rod history, and soluble boron concentration) affect the isotopic inventory of fuel that is depleted in a pressurized water reactor (PWR). However, obtaining the detailed operating histories needed to model all PWR fuel assemblies to which BUC would be applied is an onerous and costly task. Simplifications therefore have been suggested that could lead to using ''bounding'' depletion parameters that could be broadly applied to different fuel assemblies. This paper presents a method for determining a set of bounding depletion parameters for use in criticality analyses for SNF.

  5. Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: Characterization and evaluation of phase stability

    SciTech Connect

    Wilkin, Richard T.; Lee, T.R.

    2010-10-22

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation ({Delta}{sub f}G{sup o}) for chukanovite is - 1174.4 {+-} 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs.

  6. Silicon-doping in carbon nanotubes: formation energies, electronic structures, and chemical reactivity.

    PubMed

    Bian, Ruixin; Zhao, Jingxiang; Fu, Honggang

    2013-04-01

    By carrying out density functional theory (DFT) calculations, we have studied the effects of silicon (Si)-doping on the geometrical and electronic properties, as well as the chemical reactivity of carbon nanotubes (CNTs). It is found that the formation energies of these nanotubes increase with increasing tube diameters, indicating that the embedding of Si into narrower CNTs is more energetically favorable. For the given diameters, Si-doping in a (n, 0) CNT is slightly easier than that of in (n, n) CNT. Moreover, the doped CNTs with two Si atoms are easier to obtain than those with one Si atom. Due to the introduction of impurity states after Si-doping, the electronic properties of CNTs have been changed in different ways: upon Si-doping into zigzag CNTs, the band gap of nanotube is decreased, while the opening of band gap in armchair CNTs is found. To evaluate the chemical reactivity of Si-doped CNTs, the adsorption of NH3 and H2O on this kind of material is explored. The results show that N-H bond of NH3 and O-H bond of H2O can be easily split on the surface of doped CNTs. Of particular interest, the novel reactivity makes it feasible to use Si-doped CNT as a new type of splitter for NH3 and H2O bond, which is very important in chemical and biological processes. Future experimental studies are greatly desired to probe such interesting processes.

  7. Effect of aging on formation of reactive oxygen species by mitochondria of rat heart.

    PubMed

    Kuka, Stanislav; Tatarkova, Zuzana; Racay, Peter; Lehotsky, Jan; Dobrota, Dusan; Kaplan, Peter

    2013-09-01

    Mitochondrial electron transport chain is thought to be a major source of reactive oxygen species (ROS) during aging. However, this view is supported mainly by accumulation of mitochondrial oxidative damage with age and the exact sites of ROS formation remains unknown. In the present study, we measured rate of ROS formation using 2',7'-dichlorofluorescein (DCF) probe in cardiac mitochondria from adult (6-month-old), old (15-month-old) and senescent (26-month-old) rats. In mitochondria oxidizing complex II substrate, succinate, the rate of ROS formation progressively increased with age. In the presence of complex I inhibitor rotenone or complex III inhibitor antimycin A, the rate ROS formation significantly decreased, but even the combination of inhibitors could not fully prevent generation of ROS. Age-dependent increase of ROS formation was accompanied by a loss of thiol groups, tryptophan degradation and increased lipid peroxidation. These data suggest that in addition to complex I and complex II other mitochondrial sites can contribute to accelerated ROS generation and oxidative damage during aging.

  8. Anthrax edema toxin inhibits Nox1-mediated formation of reactive oxygen species by colon epithelial cells.

    PubMed

    Kim, Jun-Sub; Bokoch, Gary M

    2009-01-01

    One major route of intoxication by Bacillus anthracis (anthrax) spores is via their ingestion and subsequent uptake by the intestinal epithelium. Anthrax edema toxin (ETx) is an adenylate cyclase that causes persistent elevation of cAMP in intoxicated cells. NADPH oxidase enzymes (Nox1-Nox5, Duox1 and 2) generate reactive oxygen species (ROS) as components of the host innate immune response to bacteria, including Nox1 in gastrointestinal epithelial tissues. We show that ETx effectively inhibits ROS formation by Nox1 in HT-29 colon epithelial cells. This inhibition requires the PKA-mediated phosphorylation of the Nox1-regulatory component, NoxA1, and the subsequent binding of 14-3-3zeta. Inhibition of Nox1-mediated ROS formation in the gut epithelium may be a mechanism used by B. anthracis to circumvent the innate immune response.

  9. Controlled formation of anatase and rutile TiO2 thin films by reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Rafieian, Damon; Ogieglo, Wojciech; Savenije, Tom; Lammertink, Rob G. H.

    2015-09-01

    We discuss the formation of TiO2 thin films via DC reactive magnetron sputtering. The oxygen concentration during sputtering proved to be a crucial parameter with respect to the final film structure and properties. The initial deposition provided amorphous films that crystallise upon annealing to anatase or rutile, depending on the initial sputtering conditions. Substoichiometric films (TiOx<2), obtained by sputtering at relatively low oxygen concentration, formed rutile upon annealing in air, whereas stoichiometric films formed anatase. This route therefore presents a formation route for rutile films via lower (<500 °C) temperature pathways. The dynamics of the annealing process were followed by in situ ellipsometry, showing the optical properties transformation. The final crystal structures were identified by XRD. The anatase film obtained by this deposition method displayed high carriers mobility as measured by time-resolved microwave conductance. This also confirms the high photocatalytic activity of the anatase films.

  10. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-02-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  11. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-06-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  12. Organic chloramines in drinking water: An assessment of formation, stability, reactivity and risk.

    PubMed

    How, Zuo Tong; Linge, Kathryn L; Busetti, Francesco; Joll, Cynthia A

    2016-04-15

    Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N-chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N-chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable.

  13. Reactivity-dependent PCR: direct, solution-phase in vitro selection for bond formation.

    PubMed

    Gorin, David J; Kamlet, Adam S; Liu, David R

    2009-07-08

    In vitro selection is a key component of efforts to discover functional nucleic acids and small molecules from libraries of DNA, RNA, and DNA-encoded small molecules. Such selections have been widely used to evolve RNA and DNA catalysts and, more recently, to discover new reactions from DNA-encoded libraries of potential substrates. While effective, current strategies for selections of bond-forming and bond-cleaving reactivity are generally indirect, require the synthesis of biotin-linked substrates, and involve multiple solution-phase and solid-phase manipulations. In this work we report the successful development and validation of reactivity-dependent PCR (RDPCR), a new method that more directly links bond formation or bond cleavage with the amplification of desired sequences and that obviates the need for solid-phase capture, washing, and elution steps. We show that RDPCR can be used to select for bond formation in the context of reaction discovery and for bond cleavage in the context of protease activity profiling.

  14. Importance of thermal reactivity for hexamethylenetetramine formation from simulated interstellar ices

    NASA Astrophysics Data System (ADS)

    Vinogradoff, V.; Fray, N.; Duvernay, F.; Briani, G.; Danger, G.; Cottin, H.; Theulé, P.; Chiavassa, T.

    2013-03-01

    Context. Complex organic molecules are observed in a broad variety of astrophysical objects, but little is known about their formation mechanism. Laboratory simulations on interstellar ice analogues are therefore crucial for understanding the origin of these complex organic molecules. In this context, we focus on the thermal reactivity for the formation of the organic residue obtained after photolysis at 25 K of the interstellar ice analogue (H2O:CH3OH:NH3) warmed to 300 K. Aims: We determine the formation mechanism of one major product detected in the organic residue: hexamethylenetetramine (HMT). We compare the warming of the photolysed interstellar ice analogue with the warming of the two non-photolysed specific ice mixtures H2CO:NH3:HCOOH and CH2NH:HCOOH, which are used as references. Using both general and specific approaches, we show the precise role of the UV photons and the thermal processing in the HMT formation. Methods: We used Fourier transform infrared spectroscopy (FTIR) to monitor the chemical changes induced by the heating of the photolysed ice analogue and characterize some important species that will subsequently evolve in the formation of HMT in the residue. Results: We show that the thermal processes play a key role in the HMT formation in photolysed ice analogues heated at 300 K. We identify the stable intermediates in the HMT formation that are formed during the warming: the aminomethanol (NH2CH2OH) and the protonated ion trimethyletriamine (TMTH+, C3H10N3+). We also identify for the first time a new product in the organic residue, the polymethylenimine PMI (-(CH2 -NH)n). Results from this study will be interesting for the analysis of the forthcoming Rosetta mission.

  15. Secondary organic aerosol formation from photo-oxidation of unburned fuel: experimental results and implications for aerosol formation from combustion emissions.

    PubMed

    Jathar, Shantanu H; Miracolo, Marissa A; Tkacik, Daniel S; Donahue, Neil M; Adams, Peter J; Robinson, Allen L

    2013-11-19

    We conducted photo-oxidation experiments in a smog chamber to investigate secondary organic aerosol (SOA) formation from eleven different unburned fuels: commercial gasoline, three types of jet fuel, and seven different diesel fuels. The goals were to investigate the influence of fuel composition on SOA formation and to compare SOA production from unburned fuel to that from diluted exhaust. The trends in SOA production were largely consistent with differences in carbon number and molecular structure of the fuel, i.e., fuels with higher carbon numbers and/or more aromatics formed more SOA than fuels with lower carbon numbers and/or substituted alkanes. However, SOA production from different diesel fuels did not depend strongly on aromatic content, highlighting the important contribution of large alkanes to SOA formation from mixtures of high carbon number (lower volatility) precursors. In comparison to diesels, SOA production from higher volatility fuels such as gasoline appeared to be more sensitive to aromatic content. On the basis of a comparison of SOA mass yields (SOA mass formed per mass of fuel reacted) and SOA composition (as measured by an aerosol mass spectrometer) from unburned fuels and diluted exhaust, unburned fuels may be reasonable surrogates for emissions from uncontrolled engines but not for emissions from engines with after treatment devices such as catalytic converters.

  16. The development of reactive fuel grains for pyrophoric relight of in-space hybrid rocket thrusters

    NASA Astrophysics Data System (ADS)

    Steiner, Matthew Wellington

    This study presents and investigates a novel hybrid fuel grain that reacts pyrophorically with gaseous oxidizer to achieve restart of a hybrid rocket motor propulsion system while reducing cost and handling concerns. This reactive fuel grain (RFG) relies on the pyrophoric nature of finely divided metal particles dispersed in a solid dicyclopentadiene (DCPD) binder, which has been shown to encapsulate air-sensitive additives until they are exposed to combustion gases. An RFG is thus effectively inert in open air in the absence of an ignition source, though the particles encapsulated within remain pyrophoric. In practice, this means that an RFG that is ignited in the vacuum of space and then extinguished will expose unoxidized pyrophoric particles, which can be used to generate sufficient heat to relight the propellant when oxidizer is flowed. The experiments outlined in this work aim to develop a suitable pyrophoric material for use in an RFG, demonstrate pyrophoric relight, and characterize performance under conditions relevant to a hybrid rocket thruster. Magnesium, lithium, calcium, and an alloy of titanium, chromium, and manganese (TiCrMn) were investigated to determine suitability of pure metals as RFG additives. Additionally, aluminum hydride (AlH3), lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4), and magnesium hydride (MgH2) were investigated to determine suitability of metals hydrides as RFG additives or as precursors for pure-metal RFG additives. Pyrophoric metals have been previously investigated as additives for increasing the regression rate of hybrid fuels, but to the author's knowledge, these materials have not been specifically investigated for their ability to ignite a propellant pyrophorically. Commercial research-grade metals were obtained as coarse powders, then ball-milled to attempt to reduce particle size below a critical diameter needed for pyrophoricity. Magnesium hydride was ball-milled and then cycled in a hydride cycling

  17. Formation and reactivity of inorganic and organic chloramines and bromamines during oxidative water treatment.

    PubMed

    Heeb, Michèle B; Kristiana, Ina; Trogolo, Daniela; Arey, J Samuel; von Gunten, Urs

    2017-03-01

    The formation and further reactions of halamines during oxidative water treatment can be relevant for water quality. In this study, we investigated the formation and reactivity of several inorganic and organic halamines (monochloramine, N-chloromethylamine, N-chlorodimethylamine, monobromamine, dibromamine, N-bromomethylamine, N,N-dibromomethylamine, and N-bromodimethylamine) by kinetic experiments, transformation product analysis, and quantum chemical computations. Kinetic model simulations were conducted to evaluate the relevance of halamines for various water treatment scenarios. Halamines were quickly formed from the reaction of chlorine and bromine with ammonia or organic amines. Species-specific second-order rate constants for the reaction of chlorine and bromine with ammonia, methyl- and dimethylamine were in the order of 10(6)-10(8) M(-1)s(-1). The formed halamines were found to be reactive towards phenolic compounds, forming halogenated phenols via electrophilic aromatic substitution (phenol and resorcinol) or quinones via electron transfer (catechol and hydroquinone). At near neutral pH, apparent second-order rate constants for these reactions were in the order of 10(-4)-10(-1) M(-1)s(-1) for chloramines and 10(1)-10(2) M(-1)s(-1) for bromamines. Quantum chemical computations were used to determine previously unknown aqueous pKa values, gas phase bond dissociation energies (BDE) and partial atomic charges of the halamines, allowing a better understanding of their reactivities. Kinetic model simulations, based on the results of this study, showed that during chlorination inorganic and organic chloramines are the main halamines formed. However, their further reactions with organic matter are outcompeted kinetically by chlorine. During ozonation, mainly inorganic bromamines are formed, since ozone quickly oxidizes organic amines. The further reactions of bromamine are typically outcompeted by ozone and thus generally of minor importance. The use of

  18. Inhibitory effects of fluvastain and its metabolites on the formation of several reactive oxygen species.

    PubMed

    Nakashima, A; Ohtawa, M; Iwasaki, K; Wada, M; Kuroda, N; Nakashima, K

    2001-08-10

    We investigated the inhibitory effects of fluvastain (FV) and its metabolites (M-2, M-3, M-4, M-5, and M-7) on the formation of several reactive oxygen species (ROS), such as singlet oxygen (1O2), superoxide anion (O2-), hydroxy radical (*OH), hypochlorite ion (OCL-), and linoleic acid peroxide (LOO*). Inhibitory effects of pravastatin (PV), simvastatin (SV), probucol (PR) and alpha-tocopherol (TOC) were also tested. The inhibitory effects of 5-hydroxy FV (M-2) and 6-hydroxy FV (M-3) on the formation of 1O2, O2-, *OH, and OCL- were strongest. Scavenging of 1O2 by M-4, M-5, (+)-FV, and (-)-FV was also noted. The inhibitory effects of (+)-FV on the formation of 1O2 were comparable to those of (-)-FV, PV, SV, PR and M-7 had little or no inhibitory effect on the formation of several ROS. In conclusion, FV and its metabolites, particulary M-2 and M-3, have the potential to protect against oxidative stress mediated by several ROS.

  19. Imaging the C black formation by acetylene pyrolysis with molecular reactive force field simulations.

    PubMed

    Zhang, Chaoyang; Zhang, Chi; Ma, Yu; Xue, Xianggui

    2015-05-07

    C black is a class of substantial materials with a long history of applications. However, apart from some descriptions of primary reactions, subsequent processes leading up to the final formation mechanism remain unclear. This mechanism is also crucial for understanding the formation of other carbonaceous materials. In this work, we visualize C black formation by acetylene pyrolysis using molecular dynamics simulations with a molecular reactive force field named ReaxFF. We find that the formation undergoes four stages: (1) chain elongation by H abstraction and polymerization of small C species, (2) chain branching, (3) cyclization and ring densification, and (4) condensed ring folding. The simulated C black particle possesses a structure of folded graphite layers, which is in good accordance with experimental observations. Cyclization and condensation are derived from fusion between neighboring chains, significantly varying from common experimental observations at relatively low temperatures that abide by the mechanism of H abstraction and C2H2 addition. Moreover, polyyne and polyene are usually found during acetylene pyrolysis, suggesting that the pyrolysis of acetylene and other hydrocarbons may be a feasible method of obtaining carbyne, a novel carbonaceous material with a high value.

  20. Aflatoxin B1 Induces Reactive Oxygen Species-Mediated Autophagy and Extracellular Trap Formation in Macrophages

    PubMed Central

    An, Yanan; Shi, Xiaochen; Tang, Xudong; Wang, Yang; Shen, Fengge; Zhang, Qiaoli; Wang, Chao; Jiang, Mingguo; Liu, Mingyuan; Yu, Lu

    2017-01-01

    Aflatoxins are a group of highly toxic mycotoxins with high carcinogenicity that are commonly found in foods. Aflatoxin B1 (AFB1) is the most toxic member of the aflatoxin family. A recent study reported that AFB1 can induce autophagy, but whether AFB1 can induce extracellular traps (ETs) and the relationships among innate immune responses, reactive oxygen species (ROS), and autophagy and the ETs induced by AFB1 remain unknown. Here, we demonstrated that AFB1 induced a complete autophagic process in macrophages (MΦ) (THP-1 cells and RAW264.7 cells). In addition, AFB1 induced the generation of MΦ ETs (METs) in a dose-dependent manner. In particular, the formation of METs significantly reduced the AFB1 content. Further analysis using specific inhibitors showed that the inhibition of either autophagy or ROS prevented MET formation caused by AFB1, indicating that autophagy and ROS were required for AFB1-induced MET formation. The inhibition of ROS prevented autophagy, indicating that ROS generation occurred upstream of AFB1-induced autophagy. Taken together, these data suggest that AFB1 induces ROS-mediated autophagy and ETs formation and an M1 phenotype in MΦ. PMID:28280716

  1. Effects of uncertainty in SAPRC90 rate constants and selected product yields on reactivity adjustment factors for alternative fuel vehicle emissions. Final report

    SciTech Connect

    Bergin, M.S.; Russell, A.G.; Yang, Y.J.; Milford, J.B.; Kirchner, F.; Stockwell, W.R.

    1996-07-01

    Tropospheric ozone is formed in the atmosphere by a series of reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO{sub x}). While NOx emissions are primarily composed of only two compounds, nitrogen oxide (NO) and nitrogen dioxide (NO{sub 2}), there are hundreds of different VOCs being emitted. In general, VOCs promote ozone formation, however, the rate and extent of ozone produced by the individual VOCs varies considerably. For example, it is widely acknowledged that formaldehyde (HCHO) is a very reactive VOC, and produces ozone rapidly and efficiently under most conditions. On the other hand, VOCs such as methane, ethane, propane, and methanol do not react as quickly, and are likely to form less urban ozone than a comparable mass of HCHO. The difference in ozone forming potential is one of the bases for the use of alternative fuels. The fuels considered in this study included compressed natural gas, LPG, mixtures of methanol and gasoline, ethanol and gasoline, and a reformulated gasoline.

  2. The Effect of Chemical Reactivity and Charge Transfer on Gallium-Arsenide (110) Schottky Barrier Formation.

    NASA Astrophysics Data System (ADS)

    Williams, Michael Duryea

    Transition and near noble metals have been deposited in sequential steps on atomically clean cleaved Gallium Arsenide (GaAs) surfaces under ultra-high vacuum conditions. Soft X-ray and ultra-violet photoemission spectroscopies were used to elucidate the room temperature (RT) chemistry and Fermi level pinning behaviors of these systems. The results show that the nature or degree of the chemical reaction has little effect on the Schottky barrier (SB) height of the metal-semiconductor contact. Silver (Ag), Gold (Au), Copper (Cu) and Palladium (Pd) for example, exhibit a range of chemical reactivities with the substrate going from non-reactive in the case of Ag to very reactive for Pd. These all have a SB height of 0.9 electron volts (eV) for n-type GaAs. Nickel (Ni), Chromium (Cr) and Titanium (Ti), on the other hand, also react strongly but have a SB height of 0.7 eV. The pinning position of the Fermi level at the interface for the established barrier (with the exception of the Ag contact) is also found to be independent of whether the substrate is doped n or p-type. An examination of trends in charge transfer parameters between the metal overlayer and the substrate has led to a strong correlation between the electronegativity (Pauling's scale) of the metal and the observed SB height. It is suggested that the formation of a dipole at the interface effects a charge transfer between the adatom induced defect levels and the metal overlayer consistent with charge neutrality. As a test, two additional sets of experiments were performed. The first is a study of Ytterbium (Yb) on the GaAs suabstrate. The unique chemistry of the rare earth metal provides further proof that the SB height is independent of chemistry. The second set of experiments is a kinetic study of the development of the Aluminum (Al)/GaAs SB. The RT and low temperature ((LESSTHEQ)-50(DEGREES)C) substrates show a significant variation in the pinning behavior of the interfacial Fermi level with coverage. The

  3. The Chemistry of Deposit Formation in Distillate Fuels,

    DTIC Science & Technology

    1986-01-01

    stability. The acids - decanoic acid , furoic acid , chloroacetic acid and dodecylbenzenesulfonic acid (DBSA) - were chosen to obtain a wide range of acid ...is quite good. A qualification on two of the chloroacetic acid data points is in order. The filled circles in the figure, for insolubles formation at...the elemental analysis was the low value for chlorine (ɘ.5%) found in the deposit from chloroacetic acid doped 30/70 reference fluid. This indicates

  4. The effect of the composition of plutonium loaded on the reactivity change and the isotopic composition of fuel produced in a fast reactor

    NASA Astrophysics Data System (ADS)

    Blandinskiy, V. Yu.

    2014-12-01

    This paper presents the results of a numerical investigation into burnup and breeding of nuclides in metallic fuel consisting of a mixture of plutonium and depleted uranium in a fast reactor with sodium coolant. The feasibility of using plutonium contained in spent nuclear fuel from domestic thermal reactors and weapons-grade plutonium is discussed. It is shown that the largest production of secondary fuel and the least change in the reactivity over the reactor lifetime can be achieved when employing plutonium contained in spent nuclear fuel from a reactor of the RBMK-1000 type.

  5. The effect of the composition of plutonium loaded on the reactivity change and the isotopic composition of fuel produced in a fast reactor

    SciTech Connect

    Blandinskiy, V. Yu.

    2014-12-15

    This paper presents the results of a numerical investigation into burnup and breeding of nuclides in metallic fuel consisting of a mixture of plutonium and depleted uranium in a fast reactor with sodium coolant. The feasibility of using plutonium contained in spent nuclear fuel from domestic thermal reactors and weapons-grade plutonium is discussed. It is shown that the largest production of secondary fuel and the least change in the reactivity over the reactor lifetime can be achieved when employing plutonium contained in spent nuclear fuel from a reactor of the RBMK-1000 type.

  6. Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

    PubMed

    Li, Yinshi; Sun, Xianda; Feng, Ying

    2017-03-11

    Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm(-2) , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH(-) ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility.

  7. Soot formation in synthetic-fuel droplets. Second quarterly technical progress report

    SciTech Connect

    England, G.; Kramlich, J.; Payne, R.

    1981-04-01

    The main objective of this program is to provide detailed information on methods of minimizing soot formation during synthetic liquid fuel combustion under conditions which minimize the formation of nitric oxides. The program comprises two main tasks, Fuel Screening Studies, and Flame Studies. The purpose of the first task is to investigate the impact of fuel properties on particulate production, to establish the importance of droplet size and examine atomizer effects, and to develop techniques for surrogate fuels production. In the second task, fundamental details of soot formation from synfuel droplet combustion will be investigated in variable slip velocity configurations. This report describes technical progress during the second three-month period of program effort (January-March 1981). During this period attention has continued to be focussed on the design, construction and commissioning of experimental systems. The Task 1 tunnel furnace modification was completed and made operational, and some preliminary fuel screening studies were carried out. Similarly, construction of the controlled flow droplet reactor was completed and efforts directed towards the design and testing of diagnostic systems. Details of this work are discussed.

  8. Long-term kinetic effects and colloid formations in dissolution of LWR spent fuels

    SciTech Connect

    Ahn, T.M.

    1996-11-01

    This report evaluates continuous dissolution and colloid formation during spent-fuel performance under repository conditions in high-level waste disposal. Various observations suggest that reprecipitated layers formed on spent-fuel surfaces may not be protective. This situation may lead to continuous dissolution of highly soluble radionuclides such as C-14, Cl-36, Tc-99, I-129, and Cs-135. However, the diffusion limits of various species involved may retard dissolution significantly. For low-solubility actinides such as Pu-(239+240) or Am-(241+243), various processes regarding colloid formation have been analyzed. The processes analyzed are condensation, dispersion, and sorption. Colloid formation may lead to significant releases of low-solubility actinides. However, because there are only limited data available on matrix dissolution, colloid formation, and solubility limits, many uncertainties still exist. These uncertainties must be addressed before the significance of radionuclide releases can be determined. 118 refs.

  9. Manipulation of combustion waves in carbon-nanotube/fuel composites by highly reactive Mg nanoparticles.

    PubMed

    Lee, Kang Yeol; Hwang, Hayoung; Shin, Dongjoon; Choi, Wonjoon

    2015-10-28

    Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile synthetic method. We present complete physiochemical characterization of these composite films and evaluate the propagating velocities and real-time surface temperatures of combustion waves. Mg/MgO nanoparticles at the interface enhanced the reaction front velocity by 41%. The resulting explosive reactions supplied additional thermal energy to the chemical fuel, accelerating flame propagation. Furthermore, the surface temperatures of the composites with Mg/MgO nanoparticles were much lower, indicating how the transient heat from the reaction would ignite the unreacted fuels at lower surface temperatures despite not reaching the necessary activation energy for a chain reaction. This mechanism contributed to thermopower waves that amplified the output voltage. Furthermore, large temperature gradients due to the presence of nanoparticles increased charge transport inside the nanostructured material, due to the increased thermoelectric effects. This manipulation could contribute to the active control of interfacially driven combustion waves along nanostructured materials, yielding many potential applications.

  10. Power reactivity decrement components of a homogeneous UPu10Zr-fueled 900-MW(thermal) liquid metal reactor

    SciTech Connect

    Meneghetti, D.; Kucera, D.A.

    1989-01-01

    Linear and Doppler feedback components of the power reactivity decrement (PRD) for a 900-MW(thermal) homogeneous UPu10Zr-fueled sodium-cooled reactor have been calculated. (The PRD is the negative of the reactivity required to bring the reactor from a zero-power hot-critical condition to a given power level.) The components are further separated into power-dependent and power-to-flow-dependent parts. These delineations enhance understanding of the contributions of the components to the feedback process. The delineation also enables the PRDs for other values of coolant flows to be estimated. The linear and Doppler components of the PRD are obtained using the EBRPOCO code, which calculates detailed axially delineated contributions of the components for every subassembly of a loading configuration. Separation of the components into power and power-to-flow parts is made by calculations of the components, assuming infinite thermal conductivities to obtain the power-to-flow values. Subtractions of these from the corresponding PRD quantities give the power-dependent parts. The values of the various feedback components are compared with corresponding quantities reported for an analogous U10Zr-fueled case.

  11. The formation of reactive species having hydroxyl radical-like reactivity from UV photolysis of N-nitrosodimethylamine (NDMA): kinetics and mechanism.

    PubMed

    Kwon, Bum Gun; Kim, Jong-Oh; Namkung, Kyu Cheol

    2012-10-15

    This study focuses on the detailed mechanism by which N-nitrosodimethylamine (NDMA) is photolyzed to form oxidized products, i.e., NO(2)(-) and NO(3)(-), and reveals a key reactive species produced during the photolysis of NDMA. Under acidic conditions, NO(2)(-) formed from the photodecomposition of NDMA was more prevalent than NO(3)(-). In this result, key species for the formation of NO(2)(-) are presumably N(2)O(3) and N(2)O(4) as termination products as well as NO and O(2) as reactants. Conversely, under alkaline conditions, NO(3)(-) was more prevalent than NO(2)(-). For this result, a key species for NO(3)(-) formation is presumably peroxynitrite (ONOO(-)). A detailed mechanistic study was performed with a competition reaction (or kinetics) between NDMA and p-nitrosodimethylaniline (PNDA) probe for hydroxyl radical (OH). It is fortuitous that the second-order rate constant for NDMA with an unknown reactive species (URS) was 5.13×10(8) M(-1) s(-1), which was similar to its published value for the reaction of NDMA+OH. Our study results showed that a key reactive species generated during NDMA photo-decomposition had hydroxyl radical-like reactivity and in particular, under alkaline conditions, it is most likely ONOO(-) as a source of nitrate ion. Therefore, for the first time, we experimentally report that an URS having OH-like reactivity can be formed during photochemical NDMA decomposition. This URS could contribute to the formations of NO(2)(-) and NO(3)(-).

  12. Nicorandil prevents sirolimus-induced production of reactive oxygen species, endothelial dysfunction, and thrombus formation.

    PubMed

    Aizawa, Ken; Takahari, Youko; Higashijima, Naoko; Serizawa, Kenichi; Yogo, Kenji; Ishizuka, Nobuhiko; Endo, Koichi; Fukuyama, Naoto; Hirano, Katsuya; Ishida, Hideyuki

    2015-03-01

    Sirolimus (SRL) is widely used to prevent restenosis after percutaneous coronary intervention. However, its beneficial effect is hampered by complications of thrombosis. Several studies imply that reactive oxygen species (ROS) play a critical role in endothelial dysfunction and thrombus formation. The present study investigated the protective effect of nicorandil (NIC), an anti-angina agent, on SRL-associated thrombosis. In human coronary artery endothelial cells (HCAECs), SRL stimulated ROS production, which was prevented by co-treatment with NIC. The preventive effect of NIC on ROS was abolished by 5-hydroxydecanoate but not by 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one. NIC also inhibited SRL-induced up-regulation of NADPH oxidase subunit p22(phox) mRNA. Co-treatment with NIC and SRL significantly up-regulated superoxide dismutase 2. NIC treatment significantly improved SRL-induced decrease in viability of HCAECs. The functional relevance of the preventive effects of NIC on SRL-induced ROS production and impairment of endothelial viability was investigated in a mouse model of thrombosis. Pretreatment with NIC inhibited the SRL-induced acceleration of FeCl3-initiated thrombus formation and ROS production in the testicular arteries of mice. In conclusion, NIC prevented SRL-induced thrombus formation, presumably due to the reduction of ROS and to endothelial protection. The therapeutic efficacy of NIC could represent an additional option in the prevention of SRL-related thrombosis.

  13. H2S cytotoxicity mechanism involves reactive oxygen species formation and mitochondrial depolarisation.

    PubMed

    Eghbal, Mohammad A; Pennefather, Peter S; O'Brien, Peter J

    2004-10-15

    A number of scavengers of reactive oxygen species (ROS) were found to be protective against cell death induced by hydrogen sulfide (H2S) in isolated hepatocytes. The H2O2 scavengers alpha-ketoglutarate and pyruvate, which also act as energy substrate metabolites, were more protective against H2S toxicity than lactate which is only an energy substrate metabolite. All of these results suggest that H2S toxicity is dependent on ROS production. We measured ROS formation directly in hepatocytes using the fluorogenic dichlorofluorescin method. H2S-induced ROS formation was dose dependent and pyruvate inhibited this ROS production. Non-toxic concentrations of H2S enhanced the cytotoxicity of H2O2 generated by glucose/glucose oxidase, which was inhibited by CYP450 inibitors. Furthermore, hepatocyte ROS formation induced by H2S was decreased by CYP450 inhibitors cimetidine and benzylimidazole. These results suggest that CYP450-dependant metabolism of H2S is responsible for inducing ROS production. H2S-induced cytotoxicity was preceded by mitochondrial depolarization as measured by rhodamine 123 fluorescence. Mitochondrial depolarization induced by H2S was prevented by zinc, methionine and pyruvate all of which decreased H2S-induced cell death. Treatment of H2S poisoning may benefit from interventions aimed at minimizing ROS-induced damage and reducing mitochondrial damage.

  14. Photo-Reactive Nanogel as a Means to Tune Properties during Polymer Network Formation

    PubMed Central

    Liu, JianCheng; Rad, Ima Y.; Sun, Fang; Stansbury, Jeffrey W.

    2013-01-01

    Photo-reactive nanogels with an integrated photoinitiator-based functionality were synthesized via a Reversible Addition-Fragmentation Chain Transfer (RAFT) process. Without additional free initiators, this nanogel is capable of radical generation and initiating polymerization of a secondary monomer (i.e. dimethacrylate) that infiltrates and disperses the nanogel particles. Due to the presence of RAFT functionality and the fact that all initiating sites are initially located within the nanogel structure, gelation can be delayed by sequencing the polymerization from the nanogel to the bulk matrix. During polymerization of a nanogel-filled resin system, a progressive delay of gelation conversion from about 2 % for conventional chain growth polymerization to 18 % for the same monomer containing 20 wt% nanogel additive was achieved. A significant delay of stress development was also observed with much lower final stress achieved with the nanogel-modified systems due to the change of network formation mechanics. Compared with the nanogel-free dimethacrylate control, which contained uniformly distributed free initiator, the flexural modulus and mechanical strength results were maintained for the photopolymers with nanogel contents greater than 10 wt%. There appears to be a critical interparticle spacing of the photo-reactive nanogel that provides effective photopolymerization while providing delayed gelation and substantial stress reduction. PMID:24348753

  15. Efficient Super Energy Transfer Collisions Through Reactive-Complex Formation: H + SO2

    NASA Astrophysics Data System (ADS)

    Smith, Jonathan M.; Wilhelm, Michael J.; Ma, Jianqiang; Dai, HAI-LUNG

    2015-06-01

    Translational-to-vibrational energy transfer (ET) from a hyperthermal H atom to ambient SO2 was characterized using time-resolved Fourier transform infrared emission spectroscopy. Vibrational excitation of SO2, following collisions with H atoms containing 59 kcal/mol of kinetic energy, generated from the 193 nm photolysis of HBr, is detected in two distinct energy distributions: one with excitation predominantly at the fundamental vibrational levels is attributable to classical impulsive collisions, while the other, accounting for 80% of the excited SO2 with vibrational energy as high as 14,000 wn, is proposed to arise from the formation of a transient reactive-complex during the collision. The cross-section for this super ET collision is determined to be 0.53±0.05 Å2, or roughly 2% of all hard sphere collisions. This observation reveals that in collisions between a hyperthermal atom and an ambient molecule, for which a reactive-complex exists on the potential energy surface, a large quantity of translational energy can be transferred to the molecule with high efficiency.

  16. Conclusive evidence of abrupt coagulation inside the void during cyclic nanoparticle formation in reactive plasma

    NASA Astrophysics Data System (ADS)

    van de Wetering, F. M. J. H.; Nijdam, S.; Beckers, J.

    2016-07-01

    In this letter, we present scanning electron microscopy (SEM) results that confirm in a direct way our earlier explanation of an abrupt coagulation event as the cause for the void hiccup. In a recent paper, we reported on the fast and interrupted expansion of voids in a reactive dusty argon-acetylene plasma. The voids appeared one after the other, each showing a peculiar, though reproducible, behavior of successive periods of fast expansion, abrupt contraction, and continued expansion. The abrupt contraction was termed "hiccup" and was related to collective coagulation of a new generation of nanoparticles growing in the void using relatively indirect methods: electron density measurements and optical emission spectroscopy. In this letter, we present conclusive evidence using SEM of particles collected at different moments in time spanning several growth cycles, which enables us to follow the nanoparticle formation process in great detail.

  17. Evidence for copper-dioxygen reactivity during alpha-synuclein fibril formation.

    PubMed

    Lucas, Heather R; Debeer, Serena; Hong, Myoung-Soon; Lee, Jennifer C

    2010-05-19

    Alpha-synuclein (alpha-syn), a presynaptic protein implicated in Parkinson's disease, binds copper(II) ion (1:1) with submicromolar affinity in vitro. Insights on the molecular details of soluble- and fibrillar-Cu-alpha-syn are gained through X-ray absorption spectroscopy. Our results indicate that the copper coordination environment (3-to-4 N/O ligands, average Cu-ligand distance approximately 1.96 A) exhibits little structural rearrangement upon amyloid formation in spite of the overall polypeptide conformational change from disordered-to-beta-sheet. Interestingly, we find that some population of Cu(II)-alpha-syn reduces to Cu(I)-alpha-syn in the absence of O(2). This autoreduction event appears diminished in the presence of O(2) suggestive of preceding Cu(I)/O(2) chemistry. Evidence for generation of reactive oxygen species is obtained by the observation of new emission features attributed to dityrosine cross-links in fibrillar samples.

  18. The contribution of lubricant to the formation of particulate matter with reactivity controlled compression ignition in light-duty diesel engines

    SciTech Connect

    Storey, John Morse; Curran, Scott; Dempsey, Adam B.; Lewis, Sr., Samuel Arthur; Reitz, Rolf; Walker, N. Ryan; Wright, Chris

    2014-12-25

    Reactivity controlled compression ignition (RCCI) has been shown in single- and multi-cylinder engine research to achieve high thermal efficiencies with ultra-low NOX and soot emissions. The nature of the particulate matter (PM) produced by RCCI operation has been shown in recent research to be different than that of conventional diesel combustion and even diesel low-temperature combustion. Previous research has shown that the PM from RCCI operation contains a large amount of organic material that is volatile and semi-volatile. However, it is unclear if the organic compounds are stemming from fuel or lubricant oil. The PM emissions from dual-fuel RCCI were investigated in this study using two engine platforms, with an emphasis on the potential contribution of lubricant. Both engine platforms used the same base General Motors (GM) 1.9-L diesel engine geometry. The first study was conducted on a single-cylinder research engine with primary reference fuels (PRFs), n-heptane, and iso-octane. The second study was conducted on a four-cylinder GM 1.9-L ZDTH engine which was modified with a port fuel injection (PFI) system while maintaining the stock direct injection fuel system. Multi-cylinder RCCI experiments were run with PFI gasoline and direct injection of 2-ethylhexyl nitrate (EHN) mixed with gasoline at 5 % EHN by volume. In addition, comparison cases of conventional diesel combustion (CDC) were performed. Particulate size distributions were measured, and PM filter samples were collected for analysis of lube oil components. Triplicate PM filter samples (i.e., three individual filter samples) for both gas chromatography-mass spectroscopy (GC-MS; organic) analysis and X-ray fluorescence (XRF; metals) were obtained at each operating point and queued for analysis of both organic species and lubricant metals. Here, the results give a clear indication that lubricants do not contribute significantly to the formation of RCCI PM.

  19. The contribution of lubricant to the formation of particulate matter with reactivity controlled compression ignition in light-duty diesel engines

    DOE PAGES

    Storey, John Morse; Curran, Scott; Dempsey, Adam B.; ...

    2014-12-25

    Reactivity controlled compression ignition (RCCI) has been shown in single- and multi-cylinder engine research to achieve high thermal efficiencies with ultra-low NOX and soot emissions. The nature of the particulate matter (PM) produced by RCCI operation has been shown in recent research to be different than that of conventional diesel combustion and even diesel low-temperature combustion. Previous research has shown that the PM from RCCI operation contains a large amount of organic material that is volatile and semi-volatile. However, it is unclear if the organic compounds are stemming from fuel or lubricant oil. The PM emissions from dual-fuel RCCI weremore » investigated in this study using two engine platforms, with an emphasis on the potential contribution of lubricant. Both engine platforms used the same base General Motors (GM) 1.9-L diesel engine geometry. The first study was conducted on a single-cylinder research engine with primary reference fuels (PRFs), n-heptane, and iso-octane. The second study was conducted on a four-cylinder GM 1.9-L ZDTH engine which was modified with a port fuel injection (PFI) system while maintaining the stock direct injection fuel system. Multi-cylinder RCCI experiments were run with PFI gasoline and direct injection of 2-ethylhexyl nitrate (EHN) mixed with gasoline at 5 % EHN by volume. In addition, comparison cases of conventional diesel combustion (CDC) were performed. Particulate size distributions were measured, and PM filter samples were collected for analysis of lube oil components. Triplicate PM filter samples (i.e., three individual filter samples) for both gas chromatography-mass spectroscopy (GC-MS; organic) analysis and X-ray fluorescence (XRF; metals) were obtained at each operating point and queued for analysis of both organic species and lubricant metals. Here, the results give a clear indication that lubricants do not contribute significantly to the formation of RCCI PM.« less

  20. Nondestructive determination of plutonium mass in spent fuel: prelliminary modeling results using the passive neutron Albedo reactivity technique

    SciTech Connect

    Evans, Louise G; Tobin, Stephen J; Schear, Melissa A; Menlove, Howard O; Lee, Sang Y; Swinhoe, Martyn T

    2009-01-01

    There are a variety of motivations for quantifying plutonium (Pu) in spent fuel assemblies by means of nondestructive assay (NDA) including the following: strengthening the capability of the International Atomic Energy Agency (LAEA) to safeguard nuclear facilities, quantifying shipper/receiver difference, determining the input accountability value at pyrochemical processing facilities, providing quantitative input to burnup credit and final safeguards measurements at a long-term repository. In order to determine Pu mass in spent fuel assemblies, thirteen NDA techniques were identified that provide information about the composition of an assembly. A key motivation of the present research is the realization that none of these techniques, in isolation, is capable of both (1) quantifying the Pu mass of an assembly and (2) detecting the diversion of a significant number of rods. It is therefore anticipated that a combination of techniques will be required. A 5 year effort funded by the Next Generation Safeguards Initiative (NGSI) of the U.S. DOE was recently started in pursuit of these goals. The first two years involves researching all thirteen techniques using Monte Carlo modeling while the final three years involves fabricating hardware and measuring spent fuel. Here, we present the work in two main parts: (1) an overview of this NGSI effort describing the motivations and approach being taken; (2) The preliminary results for one of the NDA techniques - Passive Neutron Albedo Reactivity (PNAR). The PNAR technique functions by using the intrinsic neutron emission of the fuel (primarily from the spontaneous fission of curium) to self-interrogate any fissile material present. Two separate measurements of the spent fuel are made, both with and without cadmium (Cd) present. The ratios of the Singles, Doubles and Triples count rates obtained in each case are analyzed; known as the Cd ratio. The primary differences between the two measurements are the neutron energy spectrum

  1. Effects of C60 on the Photochemical Formation of Reactive Oxygen Species from Natural Organic Matter.

    PubMed

    Yin, Lijuan; Zhou, Huaxi; Lian, Lushi; Yan, Shuwen; Song, Weihua

    2016-11-01

    Buckminsterfullerenes (C60) are widely used nanomaterials that are present in surface water. The combination of C60 and humic acid (HA) generates reactive oxygen species (ROS) under solar irradiation, but this process is not well understood. Thus, the present study focused on the photochemical formation of singlet oxygen ((1)O2), hydroxyl radical (HO(•))-like species, superoxide radicals (O2(•-)), hydrogen peroxide (H2O2), and triplet excited states ((3)C60*/(3)HA*) in solutions containing both C60 and HA. The quantum yield coefficients of excited triplet states (fTMP) and apparent quantum yields of ROS were measured and compared to the calculated values, which were based on the conservative mixing model. Although C60 proved to have only a slight impact on the (1)O2 formation from HA, C60 played a key role in the inhibition of O2(•-). The photochemical formation of H2O2 followed the conservative mixing model due to the reaction of C60(•-) with HO2(•)/O2(•-), and the biomolecular reaction rate constant has been measured as (7.4 ± 0.6) × 10(6) M(-1) s(-1). The apparent fTMP was significantly lower than the calculated value, indicating that the steric effect of HA was significant in the reaction of (3)C60* with the TMP probe. In contrast, C60 did not have an effect on the photochemical formation of HO(•) from HA, suggesting that HO(•) is elevated from the hydrophilic surface of HA. The aforementioned results may be useful for predicting the photochemical influence of C60 on aqueous environments.

  2. Manipulation of combustion waves in carbon-nanotube/fuel composites by highly reactive Mg nanoparticles

    NASA Astrophysics Data System (ADS)

    Lee, Kang Yeol; Hwang, Hayoung; Shin, Dongjoon; Choi, Wonjoon

    2015-10-01

    Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile synthetic method. We present complete physiochemical characterization of these composite films and evaluate the propagating velocities and real-time surface temperatures of combustion waves. Mg/MgO nanoparticles at the interface enhanced the reaction front velocity by 41%. The resulting explosive reactions supplied additional thermal energy to the chemical fuel, accelerating flame propagation. Furthermore, the surface temperatures of the composites with Mg/MgO nanoparticles were much lower, indicating how the transient heat from the reaction would ignite the unreacted fuels at lower surface temperatures despite not reaching the necessary activation energy for a chain reaction. This mechanism contributed to thermopower waves that amplified the output voltage. Furthermore, large temperature gradients due to the presence of nanoparticles increased charge transport inside the nanostructured material, due to the increased thermoelectric effects. This manipulation could contribute to the active control of interfacially driven combustion waves along nanostructured materials, yielding many potential applications.Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile

  3. Minimizing the risk of chemically reactive metabolite formation of new drug candidates: implications for preclinical drug design.

    PubMed

    Brink, Andreas; Pähler, Axel; Funk, Christoph; Schuler, Franz; Schadt, Simone

    2016-11-27

    Many pharmaceutical companies aim to reduce reactive metabolite formation by chemical modification at early stages of drug discovery. A practice often applied is the detection of stable trapping products of electrophilic intermediates with nucleophilic trapping reagents to guide rational structure-based drug design. This contribution delineates this strategy to minimize the potential for reactive metabolite formation of clinical candidates during preclinical drug optimization, exemplified by the experience at Roche over the past decade. For the majority of research programs it was possible to proceed with compounds optimized for reduced covalent binding potential. Such optimized candidates are expected to have a higher likelihood of succeeding throughout the development processes, resulting in safer drugs.

  4. Improving Formate and Methanol Fuels: Catalytic Activity of Single Pd Coated Carbon Nanotubes

    PubMed Central

    2016-01-01

    The oxidations of formate and methanol on nitrogen-doped carbon nanotubes decorated with palladium nanoparticles were studied at both the single-nanotube and ensemble levels. Significant voltammetric differences were seen. Pd oxide formation as a competitive reaction with formate or methanol oxidation is significantly inhibited at high overpotentials under the high mass transport conditions associated with single-particle materials in comparison with that seen with ensembles, where slower diffusion prevails. Higher electro-oxidation efficiency for the organic fuels is achieved. PMID:27761299

  5. Increased Reactive Oxygen Species Formation and Oxidative Stress in Rheumatoid Arthritis

    PubMed Central

    Mateen, Somaiya; Moin, Shagufta; Khan, Abdul Qayyum; Zafar, Atif; Fatima, Naureen

    2016-01-01

    Background Rheumatoid arthritis (RA) is an autoimmune inflammatory disorder. Highly reactive oxygen free radicals are believed to be involved in the pathogenesis of the disease. In this study, RA patients were sub-grouped depending upon the presence or absence of rheumatoid factor, disease activity score and disease duration. RA Patients (120) and healthy controls (53) were evaluated for the oxidant—antioxidant status by monitoring ROS production, biomarkers of lipid peroxidation, protein oxidation and DNA damage. The level of various enzymatic and non-enzymatic antioxidants was also monitored. Correlation analysis was also performed for analysing the association between ROS and various other parameters. Methods Intracellular ROS formation, lipid peroxidation (MDA level), protein oxidation (carbonyl level and thiol level) and DNA damage were detected in the blood of RA patients. Antioxidant status was evaluated by FRAP assay, DPPH reduction assay and enzymatic (SOD, catalase, GST, GR) and non-enzymatic (vitamin C and GSH) antioxidants. Results RA patients showed a higher ROS production, increased lipid peroxidation, protein oxidation and DNA damage. A significant decline in the ferric reducing ability, DPPH radical quenching ability and the levels of antioxidants has also been observed. Significant correlation has been found between ROS and various other parameters studied. Conclusion RA patients showed a marked increase in ROS formation, lipid peroxidation, protein oxidation, DNA damage and decrease in the activity of antioxidant defence system leading to oxidative stress which may contribute to tissue damage and hence to the chronicity of the disease. PMID:27043143

  6. Ambient Fine Particulate Matter Induces Apoptosis of Endothelial Progenitor Cells Through Reactive Oxygen Species Formation

    PubMed Central

    Cui, Yuqi; Xie, Xiaoyun; Jia, Fengpeng; He, Jianfeng; Li, Zhihong; Fu, Minghuan; Hao, Hong; Liu, Ying; Liu, Jason Z.; Cowan, Peter J.; Zhu, Hua; Sun, Qinghua; Liu, Zhenguo

    2015-01-01

    Background/Aims Bone marrow (BM)-derived endothelial progenitor cells (EPCs) play a critical role in angiogenesis and vascular repair. Some environmental insults, like fine particulate matter (PM) exposure, significantly impair cardiovascular functions. However, the mechanisms for PM-induced adverse effects on cardiovascular system remain largely unknown. The present research was to study the detrimental effects of PM on EPCs and explore the potential mechanisms. Methods PM was intranasal-distilled into male C57BL/6 mice for one month. Flow cytometry was used to measure the number of EPCs, apoptosis level of circulating EPCs and intracellular reactive oxygen species (ROS) formation. Serum TNF-α and IL-1β were measured using ELISA. To determine the role of PM-induced ROS in EPC apoptosis, PM was co-administrated with the antioxidant N-acetylcysteine (NAC) in wild type mice or used in a triple transgenic mouse line (TG) with overexpression of antioxidant enzyme network (AON) composed of superoxide dismutase (SOD)1, SOD3, and glutathione peroxidase (Gpx-1) with decreased in vivo ROS production. Results PM treatment significantly decreased circulating EPC population, promoted apoptosis of EPCs in association with increased ROS production and serum TNF-α and IL-1β levels, which could be effectively reversed by either NAC treatment or overexpression of AON. Conclusion PM exposure significantly decreased circulating EPCs population due to increased apoptosis via ROS formation in mice. PMID:25591776

  7. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA

    NASA Astrophysics Data System (ADS)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.

    2009-12-01

    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite

  8. Arginine Decarboxylase expression, polyamines biosynthesis and reactive oxygen species during organogenic nodule formation in hop.

    PubMed

    Fortes, Ana M; Costa, Joana; Santos, Filipa; Seguí-Simarro, José M; Palme, Klaus; Altabella, Teresa; Tiburcio, Antonio F; Pais, Maria S

    2011-02-01

    Hop (Humulus lupulus L.) is an economically important plant species used in beer production and as a health-promoting medicine. Hop internodes develop upon stress treatments organogenic nodules which can be used for genetic transformation and micropropagation. Polyamines are involved in plant development and stress responses. Arginine decarboxylase (ADC; EC 4·1.1·19) is a key enzyme involved in the biosynthesis of putrescine in plants. Here we show that ADC protein was increasingly expressed at early stages of hop internode culture (12h). Protein continued accumulating until organogenic nodule formation after 28 days, decreasing thereafter. The same profile was observed for ADC transcript suggesting transcriptional regulation of ADC gene expression during morphogenesis. The highest transcript and protein levels observed after 28 days of culture were accompanied by a peak in putrescine levels. Reactive oxygen species accumulate in nodular tissues probably due to stress inherent to in vitro conditions and enhanced polyamine catabolism. Conjugated polyamines increased during plantlet regeneration from nodules suggesting their involvement in plantlet formation and/or in the control of free polyamine levels. Immunogold labeling revealed that ADC is located in plastids, nucleus and cytoplasm of nodular cells. In vacuolated cells, ADC immunolabelling in plastids doubled the signal of proplastids in meristematic cells. Location of ADC in different subcellular compartments may indicate its role in metabolic pathways taking place in these compartments. Altogether these data suggest that polyamines play an important role in organogenic nodule formation and represent a progress towards understanding the role played by these growth regulators in plant morphogenesis.

  9. Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

    EPA Science Inventory

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

  10. Permeability evolution of fractured limestone due to reactive flow: Observation and prediction of wormhole formation

    NASA Astrophysics Data System (ADS)

    Deng, H.; Fitts, J. P.; Crandall, D.; McIntyre, D.; Peters, C. A.

    2014-12-01

    Fractures in porous media provide preferential pathways for flow and solute transport. Their hydraulic properties are critical parameters for determining fluid migration and leakage, and are subject to alterations when exposed to reactive flow, e.g. CO2-acidfied brine in the case of carbon storage. Our previous studies have shown how mineral heterogeneity could lead to increased roughness that mitigates the increase in fracture permeability. This study shows that, even in rocks with mineral homogeneity, fracture geometry is subject to complex alterations. In this presentation, we report an experimental study of CO2-acidified brine in fractured Indiana Limestone, with comprehensive characterization of effluent chemistry analyzed by ICP-OES, and 3D geometry evolution using micro-computed topography (xCT). Significant carbonate dissolution was observed but the reaction extent revealed by the effluent chemistry was less than what was predicted by simple reaction transport models. xCT imaging revealed the formation of wormhole channels in the fracture, and the channels grew larger downstream and more prominent over time. Using the fracture geometries derived from the xCT images, we simulated the flow field and inferred the evolution of fracture hydraulic properties. To interpret the process of wormholing and its impacts on fracture hydraulic properties, we used reactive transport modeling to simulate the interplay between fracture geometry, fluid flow and geochemical reactions. Our simulations predicted that wormholes were formed in fractures with initial roughness representative of natural subsurface systems. The presence of wormholes caused a disproportionately larger permeability increase than would be expected given the extent of volume change.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  12. Computation Sheds Insight into Iron Porphyrin Carbenes' Electronic Structure, Formation, and N-H Insertion Reactivity.

    PubMed

    Sharon, Dina A; Mallick, Dibyendu; Wang, Binju; Shaik, Sason

    2016-08-03

    Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential.

  13. Impacts of powdered activated carbon addition on trihalomethane formation reactivity of dissolved organic matter in membrane bioreactor effluent.

    PubMed

    Ma, Defang; Gao, Yue; Gao, Baoyu; Wang, Yan; Yue, Qinyan; Li, Qian

    2014-12-01

    Characteristics and trihalomethane (THM) formation reactivity of dissolved organic matter (DOM) in effluents from two membrane bioreactors (MBRs) with and without powdered activated carbon (PAC) addition (referred to as PAC/MBR and MBR, respectively) were examined to investigate the effects of PAC addition on THM formation of MBR effluent during chlorination. PAC addition increased the specific UV absorbance. Hydrophobic DOM especially hydrophobic acids in PAC/MBR effluent (50%) were more than MBR effluent (42%). DOM with molecular weight <1 kDa constituted 12% of PAC/MBR effluent DOM, which was less than that of MBR effluent (16%). Data obtained from excitation and emission matrix fluorescence spectroscopy revealed that PAC/MBR effluent DOM contained more simple aromatic protein, but had less fulvic acid-like and soluble microbial by-product-like. PAC addition reduced the formation of bromine-containing THMs during chlorination of effluents, but increased THM formation reactivity of effluent DOM.

  14. Formate: an Energy Storage and Transport Bridge between Carbon Dioxide and a Formate Fuel Cell in a Single Device.

    PubMed

    Vo, Tracy; Purohit, Krutarth; Nguyen, Christopher; Biggs, Brenna; Mayoral, Salvador; Haan, John L

    2015-11-01

    We demonstrate the first device to our knowledge that uses a solar panel to power the electrochemical reduction of dissolved carbon dioxide (carbonate) into formate that is then used in the same device to operate a direct formate fuel cell (DFFC). The electrochemical reduction of carbonate is carried out on a Sn electrode in a reservoir that maintains a constant carbon balance between carbonate and formate. The electron-rich formate species is converted by the DFFC into electrical energy through electron release. The product of DFFC operation is the electron-deficient carbonate species that diffuses back to the reservoir bulk. It is possible to continuously charge the device using alternative energy (e.g., solar) to convert carbonate to formate for on-demand use in the DFFC; the intermittent nature of alternative energy makes this an attractive design. In this work, we demonstrate a proof-of-concept device that performs reduction of carbonate, storage of formate, and operation of a DFFC.

  15. Uncertainty in the reactive transport model response to analkaline perturbation in a clay formation

    SciTech Connect

    Burnol, A.; Blanc, P.; Xu, T.; Spycher, N.; Gaucher, E.C.

    2006-03-15

    The mineral alteration in the concrete barrier and in the clay formation around long-lived intermediate-level radioactive waste in the French deep geological disposal concept is evaluated using numerical modeling. There are concerns that the mineralogical composition of the surrounded clay will not be stable under the high alkaline pore fluid conditions caused by concrete (pH {approx} 12). Conversely, the infiltration of CO{sub 2}-rich groundwater from the clay formation into initially unsaturated concrete, at the high temperature (T {approx} 70 C) produced from the decay of radionuclides, could cause carbonation, thereby potentially affecting critical performance functions of this barrier. This could also lead to significant changes in porosity, which would affect aqueous diffusive transport of long-lived radionuclides. All these processes are therefore intimately coupled and advanced reactive transport models are required for long-term performance assessment. The uncertainty in predictions of these models is one major question that must be answered. A mass-transfer model response to an alkaline perturbation in clay with standard model values is first simulated using the two-phase non-isothermal reactive transport code TOUGHREACT. The selection of input parameters is thereafter designed to sample uncertainties in a wide range of physico-chemical processes without making a priori assumptions about the relative importance of different feedbacks. This 'base-case' simulation is perturbed by setting a parameter to a minimum, intermediate or maximum value or by switching on/off a process. This sensitivity analysis is conducted using grid computing facilities of BRGM (http://iggi.imag.fr). Our evaluation of the preliminary results suggests that the resaturation and the heating of the near-field will be of long enough duration to cause a limited carbonation through all the width of the concrete barrier. Another prediction is the possibility of self-sealing at the concrete

  16. Using fluorescence-activated flow cytometry to determine reactive oxygen species formation and membrane lipid peroxidation in viable boar spermatozoa

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fluorescence-activated flow cytometry analyses were developed for determination of reactive oxygen species (ROS) formation and membrane lipid peroxidation in live spermatozoa loaded with, respectively, hydroethidine (HE) or the lipophilic probe 4,4-difluoro-5-(4-phenyl-1,3-butadienyl)-4-bora-3a,4a-d...

  17. Pore Scale Modeling of the Reactive Transport of Chromium in the Cathode of a Solid Oxide Fuel Cell

    SciTech Connect

    Ryan, Emily M.; Tartakovsky, Alexandre M.; Recknagle, Kurtis P.; Khaleel, Mohammad A.; Amon, Cristina

    2011-01-01

    We present a pore scale model of a solid oxide fuel cell (SOFC) cathode. Volatile chromium species are known to migrate from the current collector of the SOFC into the cathode where over time they decrease the voltage output of the fuel cell. A pore scale model is used to investigate the reactive transport of chromium species in the cathode and to study the driving forces of chromium poisoning. A multi-scale modeling approach is proposed which uses a cell level model of the cathode, air channel and current collector to determine the boundary conditions for a pore scale model of a section of the cathode. The pore scale model uses a discrete representation of the cathode to explicitly model the surface reactions of oxygen and chromium with a cathode material. The pore scale model is used to study the reaction mechanisms of chromium by considering the effects of reaction rates, diffusion coefficients, chromium vaporization, and oxygen consumption on chromium’s deposition in the cathode. The study shows that chromium poisoning is most significantly affected by the chromium reaction rates in the cathode and that the reaction rates are a function of the local current density in the cathode.

  18. Fuel Spray and Flame Formation in a Compression-Ignition Engine Employing Air Flow

    NASA Technical Reports Server (NTRS)

    Rothrock, A M; Waldron, C D

    1937-01-01

    The effects of air flow on fuel spray and flame formation in a high-speed compression-ignition engine have been investigated by means of the NACA combustion apparatus. The process was studied by examining high-speed motion pictures taken at the rate of 2,200 frames a second. The combustion chamber was of the flat-disk type used in previous experiments with this apparatus. The air flow was produced by a rectangular displacer mounted on top of the engine piston. Three fuel-injection nozzles were tested: a 0.020-inch single-orifice nozzle, a 6-orifice nozzle, and a slit nozzle. The air velocity within the combustion chamber was estimated to reach a value of 425 feet a second. The results show that in no case was the form of the fuel spray completely destroyed by the air jet although in some cases the direction of the spray was changed and the spray envelope was carried away by the moving air. The distribution of the fuel in the combustion chamber of a compression-ignition engine can be regulated to some extent by the design of the combustion chamber, by the design of the fuel-injection nozzle, and by the use of air flow.

  19. 40 CFR 600.307-95 - Fuel economy label format requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy... dual fuel automobiles, the statement: “All fuel economy values on this label pertain to fuel usage. fuel(s) usage will yield different values. See the FREE FUEL ECONOMY GUIDE for information on .” At...

  20. Technical Note: Enhanced reactivity of nitrogenous organohalogen formation from plant litter to bacteria

    NASA Astrophysics Data System (ADS)

    Wang, J. J.; Ng, T. W.; Zhang, Q.; Yang, X. B.; Dahlgren, R. A.; Chow, A. T.; Wong, P. K.

    2012-06-01

    C1/C2 organohalogens (organohalogens with one or two carbon atoms) can have significant environmental toxicity and ecological impact, such as carcinogenesis, ozone depletion and global warming. Natural halogenation processes have been identified for a wide range of natural organic matter, including soils, plant and animal debris, algae, and fungi. Yet, few have considered these organohalogens generated from the ubiquitous bacteria, one of the largest biomass pools on Earth. Here, we report and confirm the formation of chloroform (CHCl3) dichloro-acetonitrile (CHCl2CN), chloral hydrate (CCl3CH(OH)2) and their brominated analogues by direct halogenation of seven strains of common bacteria and nine cellular monomers. Comparing different major C stocks during litter decomposition stages in terrestrial ecosystems, from plant litter, decomposed litter, to bacteria, increasing reactivity for nitrogenous organohalogen yield was observed with decreasing C/N ratio. Our results raise the possibility that natural halogenation of bacteria represents a significant and overlooked contribution to global organohalogen burdens. As bacteria are decomposers that alter the C quality by transforming organic matter pools from high to low C/N ratio and constitute a large organic N pool, the bacterial activity is expected to affect the C, N, and halogen cycling through natural halogenation reactions.

  1. Technical Note: Reactivity of C1 and C2 organohalogens formation - from plant litter to bacteria

    NASA Astrophysics Data System (ADS)

    Wang, J. J.; Ng, T. W.; Zhang, Q.; Yang, X. B.; Dahlgren, R. A.; Chow, A. T.; Wong, P. K.

    2012-10-01

    C1/C2 organohalogens (organohalogens with one or two carbon atoms) can have significant environmental toxicity and ecological impact, such as carcinogenesis, ozone depletion and global warming. Natural halogenation processes have been identified for a wide range of natural organic matter, including soils, plant and animal debris, algae, and fungi. Yet, few have considered these organohalogens generated from the ubiquitous bacteria, one of the largest biomass pools on earth. Here, we report and confirm the formation of chloroform (CHCl3) dichloro-acetonitrile (CHCl2CN), chloral hydrate (CCl3CH(OH)2) and their brominated analogues by direct halogenation of seven strains of common bacteria and nine cellular monomers. Comparing different major C stocks during litter decomposition stages in terrestrial ecosystems, from plant litter, decomposed litter, to bacteria, we found increasing reactivity for nitrogenous organohalogen yield with decreasing C/N ratio. Our results raise the possibility that natural halogenation of bacteria represents a significant and overlooked contribution to global organohalogen burdens. As bacteria are decomposers that alter the C quality by transforming organic matter pools from high to low C/N ratio and constitute a large organic N pool, the bacterial activity is expected to affect the C, N, and halogen cycling through natural halogenation reactions.

  2. Iberis amara Extract Induces Intracellular Formation of Reactive Oxygen Species and Inhibits Colon Cancer

    PubMed Central

    Plauth, Annabell; Wowro, Sylvia J.; Fischer, Cornelius; Abdel-Aziz, Heba; Sauer, Sascha

    2016-01-01

    Massively increasing global incidences of colorectal cancer require efficient treatment and prevention strategies. Here, we report unexpected anticancerogenic effects of hydroethanolic Iberis amara extract (IAE), which is known as a widely used phytomedical product for treating gastrointestinal complaints. IAE significantly inhibited the proliferation of HT-29 and T84 colon carcinoma cells with an inhibitory concentration (IC50) of 6 and 9 μg/ml, respectively, and further generated inhibitory effects in PC-3 prostate and MCF7 breast cancer cells. Inhibition of proliferation in HT-29 cells was associated with a G2/M phase cell cycle arrest including reduced expression of various regulatory marker proteins. Notably, in HT-29 cells IAE further induced apoptosis by intracellular formation of reactive oxygen species (ROS). Consistent with predictions derived from our in vitro experiments, bidaily oral gavage of 50 mg/kg of IAE over 4 weeks resulted in significant inhibition of tumor growth in a mouse HT-29 tumor xenograft model. Taken together, Iberis amara extracts could become useful alternatives for preventing and treating the progression of colon cancer. PMID:27050665

  3. Reactive impinging-flow technique for polymer-electrolyte-fuel-cell electrode-defect detection

    DOE PAGES

    Zenyuk, Iryna V.; Englund, Nicholas; Bender, Guido; ...

    2016-09-29

    Reactive impinging flow (RIF) is a novel quality-control method for defect detection (i.e., reduction in Pt catalyst loading) in gas-diffusion electrodes (GDEs) on weblines. The technique uses infrared thermography to detect temperature of a nonflammable (<4% H2) reactive mixture of H2/O2 in N2 impinging and reacting on a Pt catalytic surface. In this article, different GDE size defects (with catalyst-loading reductions of 25, 50, and 100%) are detected at various webline speeds (3.048 and 9.144 m min-1) and gas flowrates (32.5 or 50 standard L min-1). Furthermore, a model is developed and validated for the technique, and it is subsequentlymore » used to optimize operating conditions and explore the applicability of the technique to a range of defects. The model suggests that increased detection can be achieved by recting more of the impinging H2, which can be accomplished by placing blocking substrates on the top, bottom, or both of the GDE; placing a substrate on both results in a factor of four increase in the temperature differential, which is needed for smaller defect detection. Lastly, overall, the RIF technique is shown to be a promising route for in-line, high-speed, large-area detection of GDE defects on moving weblines.« less

  4. Reactive impinging-flow technique for polymer-electrolyte-fuel-cell electrode-defect detection

    NASA Astrophysics Data System (ADS)

    Zenyuk, Iryna V.; Englund, Nicholas; Bender, Guido; Weber, Adam Z.; Ulsh, Michael

    2016-11-01

    Reactive impinging flow (RIF) is a novel quality-control method for defect detection (i.e., reduction in Pt catalyst loading) in gas-diffusion electrodes (GDEs) on weblines. The technique uses infrared thermography to detect temperature of a nonflammable (<4% H2) reactive mixture of H2/O2 in N2 impinging and reacting on a Pt catalytic surface. In this paper, different GDE size defects (with catalyst-loading reductions of 25, 50, and 100%) are detected at various webline speeds (3.048 and 9.144 m min-1) and gas flowrates (32.5 or 50 standard L min-1). Furthermore, a model is developed and validated for the technique, and it is subsequently used to optimize operating conditions and explore the applicability of the technique to a range of defects. The model suggests that increased detection can be achieved by recting more of the impinging H2, which can be accomplished by placing blocking substrates on the top, bottom, or both of the GDE; placing a substrate on both results in a factor of four increase in the temperature differential, which is needed for smaller defect detection. Overall, the RIF technique is shown to be a promising route for in-line, high-speed, large-area detection of GDE defects on moving weblines.

  5. Reactive impinging-flow technique for polymer-electrolyte-fuel-cell electrode-defect detection

    SciTech Connect

    Zenyuk, Iryna V.; Englund, Nicholas; Bender, Guido; Weber, Adam Z.; Ulsh, Michael

    2016-09-29

    Reactive impinging flow (RIF) is a novel quality-control method for defect detection (i.e., reduction in Pt catalyst loading) in gas-diffusion electrodes (GDEs) on weblines. The technique uses infrared thermography to detect temperature of a nonflammable (<4% H2) reactive mixture of H2/O2 in N2 impinging and reacting on a Pt catalytic surface. In this article, different GDE size defects (with catalyst-loading reductions of 25, 50, and 100%) are detected at various webline speeds (3.048 and 9.144 m min-1) and gas flowrates (32.5 or 50 standard L min-1). Furthermore, a model is developed and validated for the technique, and it is subsequently used to optimize operating conditions and explore the applicability of the technique to a range of defects. The model suggests that increased detection can be achieved by recting more of the impinging H2, which can be accomplished by placing blocking substrates on the top, bottom, or both of the GDE; placing a substrate on both results in a factor of four increase in the temperature differential, which is needed for smaller defect detection. Lastly, overall, the RIF technique is shown to be a promising route for in-line, high-speed, large-area detection of GDE defects on moving weblines.

  6. Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Amos, Richard T.; Ulrich Mayer, K.

    2006-09-01

    In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given

  7. Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

    USGS Publications Warehouse

    Amos, Richard T.; Mayer, K. Ulrich

    2006-01-01

    In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O2 to waters otherwise depleted in O2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given

  8. Local Stoichiometry and Atomic Interdiffusion during Reactive Metal/Mercury-Cadmium-Telluride Junction Formation.

    DTIC Science & Technology

    1987-10-23

    CHART NATIONAL BUREAU OF STANDARDS- 1963-A IfP LOCAL STOICHIOMETRY AND ATOMIC INTERDIFFUSION DURING REACTIVE METAL/ MERCURY- CADMIUM -TELLURIDE...TITLE rand Subtitle) S. TYPE OF REPORT PERIOED LOCAL STOICHIOMETRY AND ATOMIC INTERDIFFUSION Interim, 1/8 DURING REACTIVE METAL/MERCURY- CADMIUM ...identliy by block nuembw) Ag, Ge and Sm overlayers on Mercury- Cadmium -Telluride surfaces exhibit widely different interface reactivity and yield a

  9. Evaluating temperature and fuel stratification for heat-release rate control in a reactivity-controlled compression-ignition engine using optical diagnostics and chemical kinetics modeling

    SciTech Connect

    Musculus, Mark P. B.; Kokjohn, Sage L.; Reitz, Rolf D.

    2015-04-23

    We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injection strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still significant

  10. Fuel swelling and interaction layer formation in the SELENIUM Si and ZrN coated U(Mo) dispersion fuel plates irradiated at high power in BR2

    NASA Astrophysics Data System (ADS)

    Leenaers, A.; Van den Berghe, S.; Koonen, E.; Kuzminov, V.; Detavernier, C.

    2015-03-01

    In the framework of the SELENIUM project two full size flat fuel plates were produced with respectively Si and ZrN coated U(Mo) particles and irradiated in the BR2 reactor at SCK•CEN. Non-destructive analysis of the plates showed that the fuel swelling profiles of both SELENIUM plates were very similar to each other and none of the plates showed signs of pillowing or excessive swelling at the end of irradiation at the highest power position (local maximum 70% 235U). The microstructural analysis showed that the Si coated fuel has less interaction phase formation at low burn-up but at the highest burn-ups, defects start to develop on the IL-matrix interface. The ZrN coated fuel, shows a virtual absence of reaction between the U(Mo) and the Al, up to high fission densities after which the interaction layer formation starts and defects develop in the matrix near the U(Mo) particles. It was found and is confirmed by the SELENIUM (Surface Engineering of Low ENrIched Uranium-Molybdenum) experiment that there are two phenomena at play that need to be controlled: the formation of an interaction layer and swelling of the fuel. As the interaction layer formation occurs at the U(Mo)-matrix interface, applying a diffusion barrier (coating) at that interface should prevent the interaction between U(Mo) and the matrix. The U(Mo) swelling, observed to proceed at an accelerating rate with respect to fission density accumulation, is governed by linear solid state swelling and fission gas bubble swelling due to recrystallization of the fuel. The examination of the SELENIUM fuel plates clearly show that for the U(Mo) dispersion fuel to be qualified, the swelling rate at high burn-up needs to be reduced.

  11. Pyrite-driven reactive oxygen species formation in simulated lung fluid: implications for coal workers' pneumoconiosis.

    PubMed

    Harrington, Andrea D; Hylton, Shavonne; Schoonen, Martin A A

    2012-08-01

    The origin of coal worker's pneumoconiosis (CWP) has been long debated. A recent epidemiological study shows a correlation between what is essentially the concentration of pyrite within coal and the prevalence of CWP in miners. Hydrogen peroxide and hydroxyl radical, both reactive oxygen species (ROS), form as byproducts of pyrite oxidative dissolution in air-saturated water. Motivated by the possible importance of ROS in the pathogenesis of CWP, we conducted an experimental study to evaluate if ROS form as byproducts in the oxidative dissolution of pyrite in simulated lung fluid (SLF) under biologically applicable conditions and to determine the persistence of pyrite in SLF. While the rate of pyrite oxidative dissolution in SLF is suppressed by 51% when compared to that in air-saturated water, the initial amount of hydrogen peroxide formed as a byproduct in SLF is nearly doubled. Hydroxyl radical is also formed in the experiments with SLF, but at lower concentrations than in the experiments with water. The formation of these ROS indicates that the reaction mechanism for pyrite oxidative dissolution in SLF is no different from that in water. The elevated hydrogen peroxide concentration in SLF suggests that the decomposition, via the Fenton mechanism to hydroxyl radical or with Fe(III) to form water and molecular oxygen, is initially inhibited by the presence of SLF components. On the basis of the oxidative dissolution rate of pyrite measured in this paper, it is calculated that a respirable two micron pyrite particle will take over 3 years to dissolve completely.

  12. Formation of glutathione conjugates by reactive metabolites of vinylidene chloride in microsomes and isolated hepatocytes

    SciTech Connect

    Liebler, D.C.; Meredith, M.J.; Guengerich, F.P.

    1985-01-01

    Oxidation of the vinyl halide carcinogen and hepatotoxin vinylidene chloride (VDC) by microsomal cytochrome P-450 yields 2,2-dichloroacetaldehyde, 2-chloroacetyl chloride, 2-chloroacetic acid, and 1,1-dichloroethylene oxide. The roles of these metabolites in covalent modification of proteins and reduced glutathione (GSH) were examined. 2-Chloroacetyl chloride reacted with model thiols at least 10(3)-fold faster than did 1,1-dichloroethylene oxide and at least 10(5)-fold faster than did 2,2-dichloroacetaldehyde or 2-chloroacetic acid. Microsomal covalent binding of (/sup 14/C)VDC was inhibited by GSH but not by lysine, suggesting that protein thiols, rather than amino groups, are major targets. Liver microsomes catalyzed the formation of three GSH:VDC metabolite conjugates, identified as S-(2,2-dichloro-1-hydroxy)ethylglutathione, 2-(S-glutathionyl)acetate, and S-(2-glutathionyl)acetylglutathione, a novel conjugate containing both stable (thioether) and labile (thioester) linkages. The latter two conjugates also were formed in isolated rat hepatocytes and measurable amounts of 2-(S-glutathionyl)acetate were released into the incubation medium. Both 2-(S-glutathionyl)acetate and S-(2-glutathionyl)acetylglutathione were formed with (/sup 35/S)GSH added to the hepatic medium, indicating that reactive VDC metabolites are capable of crossing the plasma membrane to react with extracellular targets. Unlabeled S-(2-glutathionyl)-acetylglutathione underwent carbonyl substitution with added (/sup 35/S)GSH, suggesting that this conjugate may participate in modification of protein thiols. This conjugate also underwent hydrolysis with a half-life of approximately 3 hr. GSH:VDC metabolite conjugates may serve as accessible models for labile covalent adducts formed between VDC metabolites and protein thiols.

  13. Cell respiration and formation of reactive oxygen species: facts and artefacts.

    PubMed

    Nohl, H; Kozlov, A V; Gille, L; Staniek, K

    2003-12-01

    It is generally taken as an established fact that mitochondrial respiration is associated with the generation of small amounts of ROS (reactive oxygen species). There are many arguments supporting this side activity. A major argument is the particular physico-chemical configuration of dioxygen, which prevents the transfer of a pair of electrons. Instead, oxygen is reduced by the successive transfer of single electrons, necessarily leading to intermediates with odd electrons. The high rate of turnover of oxygen in the respiratory chain in combination with the existence of single-electron carriers supports the concept of mitochondria as the major cellular ROS generator. Experimental evidence on the ability of mitochondria to generate ROS was, however, based essentially on in vitro experiments with isolated mitochondria. A variety of structural and functional alterations associated with the removal of mitochondria from the cell, as well as the routinely applied ROS detection methods, may lead to artefactual deviation of odd electrons to dioxygen. We therefore checked these correlations in view of ROS formation, including the often reported effect of the membrane potential on the establishment of a redox couple with oxygen out of sequence. For this purpose we developed novel methods to prove the authenticity of mitochondria for ROS generation in the living cell. Based on our experiments, we can exclude spontaneous release of ROS from mitochondria. However, we describe conditions under which mitochondria can be transformed to mild ROS generators. The site of single-electron deviation to dioxygen was found to be ubiquinol interacting with the Rieske iron-sulphur protein and low-potential cytochrome b of the bc (1) complex.

  14. Evaluation of fuel injection configurations to control carbon and soot formation in small GT combustors

    NASA Technical Reports Server (NTRS)

    Rosfjord, T. J.; Briehl, D.

    1982-01-01

    An experimental program to investigate hardware configurations which attempt to minimize carbon formation and soot production without sacrificing performance in small gas turbine combustors has been conducted at the United Technologies Research Center. Four fuel injectors, embodying either airblast atomization, pressure atomization, or fuel vaporization techniques, were combined with nozzle air swirlers and injector sheaths, and evaluated at test conditions which included and extended beyond standard small gas turbine combustor operation. Extensive testing was accomplished with configurations embodying either a spill return or a T-vaporizer injector. Minimal carbon deposits were observed on the spill return nozzle for tests using either Jet A or ERBS test fuel. A more extensive film of soft carbon was observed on the vaporizer after operation at standard engine conditions, with large carbonaceous growths forming on the device during off-design operation at low combustor inlet temperature. Test results indicated that smoke emission levels depended on the combustor fluid mechanics (especially the mixing rates near the injector), the atomization quality of the injector and the fuel hydrogen content.

  15. Partial reactivation of a huge deep-seated ancient rock slide: recognition, formation mechanism, and stability

    NASA Astrophysics Data System (ADS)

    Tang, Minggao; Xu, Qiang; Li, Yusheng; Huang, Runqiu; Rengers, Niek; Zhu, Xing

    2016-08-01

    About 18 years ago, a large-scale discontinuous layer in properties and colour was found in the new Fengjie town at the shore of the Three Gorges Reservoir area in China. There are many resettled residents and buildings on the sloping area, the safety of which is potentially affected by this layer, so it has become the focus of attention. Before this study started there were two viewpoints regarding the origin of this layer. One was that is was from a huge ancient slide and the other was that is was from a fault graben. In order to find out how it was formed and to be able to carry out a stability analysis of the slope the authors have carried out a research program, including geological field investigations and mapping, a deep drilling hole, a geotechnical centrifuge model test, and a simulation analysis. The results of the research led to the conclusion that the layer is the sliding plane of a huge deep-seated ancient rock slide, which we called the Sanmashan landslide. An important argument for the conclusion is the recognition of a regional compressive tectonic stress field in this area, which cannot lead to the formation of a fault graben because it needs a tensional tectonic stress field. Moreover, numerous unique geological features, sliding marks, and other relics of the ancient slide have been discovered in the field. The formation process of the ancient slide could be repeated in a large geotechnical centrifuge model test. The test shows that a deformation and failure process of "creep-crack-cut" has occurred. The type of the ancient slide can be classified as a "successive rotational rock slide". Finally, the role of seepage in the stability of the Sanmashan landslide has been analysed. Our final conclusions are that, during rainfall and filling-drawdown cycles in the Three Gorges Reservoir, the Sanmashan landslide as a whole is dormant and stable and the secondary landslides in the toe area of the slope are presently stable but can be reactivated. This

  16. Mechanism of Pinhole Formation in Membrane Electrode Assemblies for PEM Fuel Cells

    NASA Technical Reports Server (NTRS)

    Stanic, Vesna; Hoberecht, Mark

    2004-01-01

    The pinhole formation mechanism was studied with a variety of MEAs using ex-situ and in-situ methods. The ex-situ tests included the MEA aging in oxygen and MEA heat of ignition. In-situ durability tests were performed in fuel cells at different operating conditions with hydrogen and oxygen. After the in-situ failure, MEAs were analyzed with an Olympus BX 60 optical microscope and Cambridge 120 scanning electron microscope. MEA chemical analysis was performed with an IXRF EDS microanalysis system. The MEA failure analyses showed that pinholes and tears were the MEA failure modes. The pinholes appeared in MEA areas where the membrane thickness was drastically reduced. Their location coincided with the stress concentration points, indicating that membrane creep was responsible for their formation. Some of the pinholes detected had contaminant particles precipitated within the membrane. This mechanism of pinhole formation was correlated to the polymer blistering.

  17. Miniature fuel cell with monolithically fabricated Si electrodes - Alloy catalyst formation -

    NASA Astrophysics Data System (ADS)

    Ogura, Daiki; Suzuki, Takahiro; Katayama, Noboru; Dowaki, Kiyoshi; Hayase, Masanori

    2013-12-01

    A novel Pd-Pt catalyst formation process was proposed for reduction of Pt usage. In our miniature fuel cells, porous Pt was used as the catalyst, and the Pt usage was quite high. To reduce the Pt usage, we have attempted to deposit Pt on porous Pd by galvanic replacement, and relatively large output was demonstrated. In this study, in order to reduce more Pt usage and explore the alloy catalyst formation process, atomic layer deposition by UPD-SLRR (Under Potential Deposition - Surface Limited Redox Replacement) was applied to the Pd-Pt catalyst formation. The new process was verified at each process steps by EDS elemental analysis, and the expected spectra were obtained. Prototype cells were constructed by the new process, and cell output was raised to 420mW/cm2 by the Pd-Pt catalyst from 125mW/cm2 with Pd catalyst.

  18. Mitigation of reactive metabolite formation for a series of 3-amino-2-pyridone inhibitors of Bruton's tyrosine kinase (BTK).

    PubMed

    Lou, Yan; Lopez, Francisco; Jiang, Yongying; Han, Xiaochun; Brotherton, Chris; Billedeau, Roland; Gabriel, Steve; Gleason, Shelly; Goldstein, David M; Hilgenkamp, Ramona; Kocer, Buelent; Orzechowski, Lucja; Tan, Jenny; Wovkulich, Peter; Wen, Bo; Fry, David; Di Lello, Paola; Chen, Lucy; Zhang, Fang-Jie; Fretland, Jennifer; Nangia, Anjali; Yang, Tian; Owens, Timothy D

    2017-02-01

    Reactive metabolites have been putatively linked to many adverse drug reactions including idiosyncratic toxicities for a number of drugs with black box warnings or withdrawn from the market. Therefore, it is desirable to minimize the risk of reactive metabolite formation for lead molecules in optimization, in particular for non-life threatening chronic disease, to maximize benefit to risk ratio. This article describes our effort in addressing reactive metabolite issues for a series of 3-amino-2-pyridone inhibitors of BTK, e.g. compound 1 has a value of 459pmol/mg protein in the microsomal covalent binding assay. Parallel approaches were taken to successfully resolve the issues: establishment of a predictive screening assay with correlation association of covalent binding assay, identification of the origin of reactive metabolite formation using MS/MS analysis of HLM as well as isolation and characterization of GSH adducts. This ultimately led to the discovery of compound 7 (RN941) with significantly reduced covalent binding of 26pmol/mg protein.

  19. Measurement of the atmospheric reactivity of emissions from gasoline and alternative-fueled vehicles: Assessment of available methodologies. Part 1. Indoor smog chamber study of reactivity. Final report for the first year, January 1-December 31, 1993

    SciTech Connect

    Kelly, N.A.; Wang, P.; Japar, S.M.; Hurley, M.D.; Wallington, T.J.

    1994-06-30

    A set of multiple indoor smog chambers were used to measure the increase in smog formation (smog = NO oxidation + O3 formation) from a series of individual test volatile organic compounds (VOC`s), as well as carbon monoxide (CO), when they were added to a standard urban mixture and irradiated for 10-12 hours with a solar simulator. The chambers and the mixtures were designed to simulate the Carter incremental reactivity concept that is being used in California. The test compounds covered a wide range of mechanistic uncertainties and predicted reactivities (reactivity is the increase in smog divided by the amount of test compound added). Also, the chambers were used to test the recently developed Integrated Empirical Rate (IER) Model which predicts that the smog formation of a mixture is constant and independent of NOx in the so-called light-limited regime.

  20. Phase Formation and Transformations in Transmutation Fuel Materials for the LIFE Engine Part I - Path Forward

    SciTech Connect

    Turchi, P E; Kaufman, L; Fluss, M J

    2008-11-10

    The current specifications of the LLNL fusion-fission hybrid proposal, namely LIFE, impose severe constraints on materials, and in particular on the nuclear fissile or fertile nuclear fuel and its immediate environment. This constitutes the focus of the present report with special emphasis on phase formation and phase transformations of the transmutation fuel and their consequences on particle and pebble thermal, chemical and mechanical integrities. We first review the work that has been done in recent years to improve materials properties under the Gen-IV project, and with in particular applications to HTGR and MSR, and also under GNEP and AFCI in the USA. Our goal is to assess the nuclear fuel options that currently exist together with their issues. Among the options, it is worth mentioning TRISO, IMF, and molten salts. The later option will not be discussed in details since an entire report is dedicated to it. Then, in a second part, with the specific LIFE specifications in mind, the various fuel options with their most critical issues are revisited with a path forward for each of them in terms of research, both experimental and theoretical. Since LIFE is applicable to very high burn-up of various fuels, distinctions will be made depending on the mission, i.e., energy production or incineration. Finally a few conclusions are drawn in terms of the specific needs for integrated materials modeling and the in depth knowledge on time-evolution thermochemistry that controls and drastically affects the performance of the nuclear materials and their immediate environment. Although LIFE demands materials that very likely have not yet been fully optimized, the challenge are not insurmountable and a well concerted experimental-modeling effort should lead to dramatic advances that should well serve other fission programs such as Gen-IV, GNEP, AFCI as well as the international fusion program, ITER.

  1. Formation and reactivation ages of a lunar mare ridge in northern Imbrium

    NASA Astrophysics Data System (ADS)

    Daket, Yuko; Yamaji, Atsushi; Sato, Katsushi; Morota, Tomokatsu; Haruyama, Junichi; Ohtake, Makiko; Matsunaga, Tsuneo

    2013-04-01

    Mare ridges and lobate scarps are the manifestations of ancient or recent horizontal compression in the shallow part of the Moon. Regional and global stress fields have been controlled possibly by mascon loading (e.g., Solomon and Head, 1980) and/or global cooling, the latter of which is affected by the origin of the Moon (e.g., Prichard and Stevenson, 2000). On the other hand, mascon loading results in tectonic deformations immediately after the deposition of mare fills (Mohit and Phillips, 2006). Therefore, the timing of deformations is a clue to distinguish the mechanisms. We constrained the formation age of a mare ridge in northern Mare Imbrium as follows. Mare basalts were so inviscid that their lava fields have level surfaces. And, lava flows would have been dammed by pre-existing mare ridges. Therefore, the depositional ages of the mare units-the one involved in the ridge and the other dammed by the ridge, indicate the range of the formation age of the ridge. Using images taken by SELENE (Kaguya), we found such an ENE-WSW trending ridge in northern Imbrium with the height, width and length of 300-400 m, 30 km and ~150 km, respectively. We defined spectrally distinctive two basaltic units in this area: Ti-poor basalt makes up the ridge, and relatively Ti-rich one lies on the plain at the foot of the ridge. Their boundary runs along the southern foot of the ridge. There are no fissures along the boundary that could have fed the Ti-rich basalt. Their model ages were estimated by crater-size frequency distribution measurements using craters of 250 m to 1 km in diameter. As a result, the Ti-poor and Ti-rich units gave the ages at 2.97 +0.16/-0.23 and 2.07 +0.17/-0.17 Ga, respectively, indicating the ridge was formed between ~3.0 and ~2.0 Ga. The majority of mare basalts in mare Imbrium were deposited before ~3.0 Ga (Solomon and Head, 1980), indicating that the ridge formation is explained as a latest event of the mascon loading. However, the unit boundary does

  2. Characteristics and trihalomethane formation reactivity of dissolved organic matter in effluents from membrane bioreactors with and without filamentous bulking.

    PubMed

    Xia, Chufan; Ma, Defang; Gao, Baoyu; Hu, Xinxiao; Yue, Qinyan; Meng, Yingjie; Kang, Shuyu; Zhang, Bei; Qi, Yuanfeng

    2016-07-01

    In this study, synthetic wastewater was treated by two identical membrane bioreactors (MBRs): the normal sludge MBR (NS-MBR) and the bulking sludge MBR (BS-MBR). Effects of filamentous bulking on the characteristics and trihalomethane (THM) formation reactivity of MBR effluent dissolved organic matter (EfOM) were investigated. Filamentous sludge bulking had no significant influence on the regulated MBR effluent water quality except NO2-N and NO3-N. NS-MBR effluent had more low molecular weight (LMW) (<5kDa) EfOM (92.43%) than BS-MBR (75.18%). About two-thirds of EfOM from BS-MBR were hydrophilic substances. On the contrary, EfOM from NS-MBR exhibited higher hydrophobicity. The ratio of polysaccharides and proteins in MBR effluents increased after filamentous bulking. There were more protein-like materials, fulvic acid-like and humic acid-like in BS-MBR EfOM. The THM formation reactivity of BS-MBR EfOM was 30.15% of NS-MBR EfOM, whereas BS-MBR EfOM exhibited higher formation reactivity of bromine containing species.

  3. Reactivity of atomically dispersed Pt(2+) species towards H2: model Pt-CeO2 fuel cell catalyst.

    PubMed

    Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi; Neitzel, Armin; Skála, Tomáš; Negreiros, Fabio R; Vorokhta, Mykhailo; Tsud, Nataliya; Prince, Kevin C; Fabris, Stefano; Neyman, Konstantin M; Matolín, Vladimír; Libuda, Jörg

    2016-03-21

    The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction.

  4. Reactive-transport model for the prediction of the uniform corrosion behaviour of copper used fuel containers

    NASA Astrophysics Data System (ADS)

    King, F.; Kolar, M.; Maak, P.

    2008-09-01

    Used fuel containers in a deep geological repository will be subject to various forms of corrosion. For containers made from oxygen-free, phosphorus-doped copper, the most likely corrosion processes are uniform corrosion, underdeposit corrosion, stress corrosion cracking, and microbiologically influenced corrosion. The environmental conditions within the repository are expected to evolve with time, changing from warm and oxidizing initially to cool and anoxic in the long-term. In response, the corrosion behaviour of the containers will also change with time as the repository environment evolve. A reactive-transport model has been developed to predict the time-dependent uniform corrosion behaviour of the container. The model is based on an experimentally-based reaction scheme that accounts for the various chemical, microbiological, electrochemical, precipitation/dissolution, adsorption/desorption, redox, and mass-transport processes at the container surface and in the compacted bentonite-based sealing materials within the repository. Coupling of the electrochemical interfacial reactions with processes in the bentonite buffer material allows the effect of the evolution of the repository environment on the corrosion behaviour of the container to be taken into account. The Copper Corrosion Model for Uniform Corrosion predicts the time-dependent corrosion rate and corrosion potential of the container, as well as the evolution of the near-field environment.

  5. Enhancement in dibenzothiophene reactive adsorption from liquid fuel via incorporation of sulfur heteroatoms into the nanoporous carbon matrix.

    PubMed

    Seredych, Mykola; Khine, Monmon; Bandosz, Teresa J

    2011-01-17

    Adsorption of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) from simulated diesel fuel was investigated with polymer-derived carbon matrices. Sulfur was incorporated to the carbon surface via a high-temperature hydrogen sulfide reduction of oxygen-containing groups. The resultant carbons were characterized by nitrogen adsorption, thermal analysis, potentiometric titration, and elemental analysis. The selectivities for DBT and DMDBT adsorption were calculated with reference to naphthalene. The carbon matrices studied had comparable structures, hence, the effects of the sulfur functionalities were evident in an increase in dibenzothiophenes selectivity and the breakthrough capacity; this was especially visible at a breakthrough point where small pores are expected to be active in the adsorption process. Incorporation of sulfur atoms into the aromatic rings of the carbon matrix increases the ability of the surface to attract dibenzothiophenes via dispersive interactions (sulfur-sulfur bridges). Sulfur and sulfur-oxygen groups present in larger pores enhance the amount of adsorbed dibenzothiophenes via specific acid-base and polar interactions. They also contribute to the reactive adsorption of DBT and DMDBT (oxidized) and their chemisorption on the carbon surface.

  6. Experimental Investigation of Fuel-Reactivity Controlled Compression Ignition (RCCI) Combustion Mode in a Multi-Cylinder, Light-Duty Diesel Engine

    SciTech Connect

    Cho, Kukwon; Curran, Scott; Prikhodko, Vitaly Y; Sluder, Scott; Parks, II, James E; Wagner, Robert M

    2011-01-01

    An experimental study was performed to provide the combustion and emission characteristics resulting from fuel-reactivity controlled compression ignition (RCCI) combustion mode utilizing dual-fuel approach in a light-duty, multi-cylinder diesel engine. In-cylinder fuel blending using port fuel injection of gasoline before intake valve opening (IVO) and early-cycle, direct injection of diesel fuel was used as the charge preparation and fuel blending strategy. In order to achieve the desired auto-ignition quality through the stratification of the fuel-air equivalence ratio ( ), blends of commercially available gasoline and diesel fuel were used. Engine experiments were performed at an engine speed of 2300rpm and an engine load of 4.3bar brake mean effective pressure (BMEP). It was found that significant reduction in both nitrogen oxide (NOx) and particulate matter (PM) was realized successfully through the RCCI combustion mode even without applying exhaust gas recirculation (EGR). However, high carbon monoxide (CO) and hydrocarbon (HC) emissions were observed. The low combustion gas temperature during the expansion and exhaust processes seemed to be the dominant source of high CO emissions in the RCCI combustion mode. The high HC emissions during the RCCI combustion mode could be due to the increased combustion quenching layer thickness as well as the -stratification at the periphery of the combustion chamber. The slightly higher brake thermal efficiency (BTE) of the RCCI combustion mode was observed than the other combustion modes, such as the conventional diesel combustion (CDC) mode, and single-fuel, premixed charge compression ignition (PCCI) combustion mode. The parametric study of the RCCI combustion mode revealed that the combustion phasing and/or the peak cylinder pressure rise rate of the RCCI combustion mode could be controlled by several physical parameters premixed ratio (rp), intake swirl intensity, and start of injection (SOI) timing of directly

  7. Medium-temperature solid oxide fuel cells prepared using reactive magnetron sputtering. Ph.D. Thesis

    SciTech Connect

    Wang, L.

    1993-12-31

    The purpose of this research is to investigate the deposition, structure, interfacial impedances, and characteristics of medium temperature solid-oxide fuel cells (SOFC`s) with thin-film electrolytes. Three main areas have been investigated. First, the structure, chemistry, and properties of materials designed specifically for medium temperature SOFC`s have been studied. The authors have developed techniques for sputter deposition of cubic 10 mol percent Y2O3-stabilized zirconia (YSZ) and 30 mol percent Y2O3-doped bismuth oxide (YSB) thin film oxygen ion conductors. The electrical properties of the films were characterized using the complex impedance spectroscopy method. Studies of AgYSZ cermet and Ag-perovskite (perovskite = La(1-x)Sr(x)Co(Mn)O3), used as high conductivity, low overpotential air electrodes, have also been carried out. Second, interfacial impedances for various electrode-electrolyte combinations and for multilayer electrolytes have been studied. In particular, the authors have found that a layer of Y-stabilized Bi2O3 (YSB) as thin as 60 nm between the YSZ electrolyte and the electrode significantly reduces the interfacial resistance. For example, inserting YSB between YSZ and a Ag-YSZ electrode reduces the resistance from 1.5 to 0.45 Omega cm(exp 2) at 750 deg C in air. Ag-(La,Sr)CoO3 on YSB electrolytes had interfacial resistances as low as 0.3 Omega cm2, compared with 0.4 and 1.5 Omega cm(exp 2) for (La,Sr)CoO3 and Ag on YSB at 750 deg C, respectively. The Ag cermet materials thus exhibited lower interfacial resistances than their component materials. Third, thin film medium temperature SOFC`s have been fabricated and characterized. SOFC`s were deposited onto porous alumina supports. The resulting cell open-circuit voltages (OCV) were approximately equal to 0.8 V, 0.3 V less than expected, due to gas cross-over.

  8. Chemical mechanistic approaches for the suppression of soot formation in the combustion of high energy density fuels. Final technical report

    SciTech Connect

    Santoro, R.J.

    1996-09-01

    Significant advantages can be gained by the use of high energy density fuels in volume limited applications. However, excessive soot formation that accompanies the combustion of these fuels presently limits their application. Fuel additive approaches prove attractive as they require minimal modifications to already existing equipment. In the present study, a variety of flame configurations were used to study the additive effects on soot formation. Through tests conducted on laminar diffusion flames carbon disulfide (CS2) and methanol (CH3OH) were found to be the most effective soot suppressants. Chemical interaction by either additive was found to far surpass the physical influences. However, the exact nature of the chemical action could not be established with the current set of experiments. Additionally, both of these additives were found to reduce soot formation in at least one high energy density fuel - quadricyclane (C7H8). To further validate this approach, studies were conducted using droplet flames and high-pressure spray flames.

  9. Synergistic effect of mixing dimethyl ether with methane, ethane, propane, and ethylene fuels on polycyclic aromatic hydrocarbon and soot formation

    SciTech Connect

    Yoon, S.S.; Anh, D.H.; Chung, S.H.

    2008-08-15

    Characteristics of polycyclic aromatic hydrocarbon (PAH) and soot formation in counterflow diffusion flames of methane, ethane, propane, and ethylene fuels mixed with dimethyl ether (DME) have been investigated. Planar laser-induced incandescence and fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that even though DME is known to be a clean fuel in terms of soot formation, DME mixture with ethylene fuel increases PAH and soot formation significantly as compared to the pure ethylene case, while the mixture of DME with methane, ethane, and propane decreases PAH and soot formation. Numerical calculations adopting a detailed kinetics showed that DME can be decomposed to produce a relatively large number of methyl radicals in the low-temperature region where PAH forms and grows; thus the mixture of DME with ethylene increases CH{sub 3} radicals significantly in the PAH formation region. Considering that the increase in the concentration of O radicals is minimal in the PAH formation region with DME mixture, the enhancement of PAH and soot formation in the mixture flames of DME and ethylene can be explained based on the role of methyl radicals in PAH and soot formation. Methyl radicals can increase the concentration of propargyls, which could enhance incipient benzene ring formation through the propargyl recombination reaction and subsequent PAH growth. Thus, the result substantiates the importance of methyl radicals in PAH and soot formation, especially in the PAH formation region of diffusion flames. (author)

  10. 78 FR 73566 - Standard Format and Content for a License Application for an Independent Spent Fuel Storage...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-06

    ... COMMISSION Standard Format and Content for a License Application for an Independent Spent Fuel Storage... public comment draft regulatory guide (DG), DG-3042, ``Standard Format and Content for a License... Waste'' (Ref. 1), Subpart B, ``License Application, Form, and Contents,'' specifies the information...

  11. Formation of industrial mixed culture biofilm in chlorophenol cultivated medium of microbial fuel cell

    NASA Astrophysics Data System (ADS)

    Hassan, Huzairy; Jin, Bo; Dai, Sheng; Ngau, Cornelius

    2016-11-01

    The formation of microbial biofilm while maintaining the electricity output is a challenging topic in microbial fuel cell (MFC) studies. This MFC critical factor becomes more significant when handling with industrial wastewater which normally contains refractory and toxic compounds. This study explores the formation of industrial mixed culture biofilm in chlorophenol cultivated medium through observing and characterizing microscopically its establishment on MFC anode surface. The mixed culture was found to develop its biofilm on the anode surface in the chlorophenol environment and established its maturity and dispersal stages with concurrent electricity generation and phenolic degradation. The mixed culture biofilm engaged the electron transfer roles in MFC by generating current density of 1.4 mA/m2 and removing 53 % of 2,4-dichlorophenol. The results support further research especially on hazardous wastewater treatment using a benign and sustainable method.

  12. Fluid mechanics simulation of fog formation associated with polluted atmosphere produced by energy related fuel combustion

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Liaw, G. S.

    1980-01-01

    It is noted that large quantities of atmospheric aerosols with composition SO4(-2), NO3(-1), and NH4(+1) have been detected in highly industrialized areas. Most aerosol products come from energy-related fuel combustion. Fluid mechanics simulation of both microphysical and macrophysical processes is considered in studying the time dependent evolution of the saturation spectra of condensation nuclei associated with polluted and clean atmospheres during the time periods of advection fog formation. The results demonstrate that the condensation nuclei associated with a polluted atmosphere provide more favorable conditions than condensation nuclei associated with a clean atmosphere to produce dense advection fog, and that attaining a certain degree of supersaturation is not necessarily required for the formation of advection fog having condensation nuclei associated with a polluted atmosphere.

  13. Methods and apparatuses for reagent delivery, reactive barrier formation, and pest control

    DOEpatents

    Gilmore, Tyler [Pasco, WA; Kaplan, Daniel I [Aiken, SC; Last, George [Richland, WA

    2002-07-09

    A reagent delivery method includes positioning reagent delivery tubes in contact with soil. The tubes can include a wall that is permeable to a soil-modifying reagent. The method further includes supplying the reagent in the tubes, diffusing the reagent through the permeable wall and into the soil, and chemically modifying a selected component of the soil using the reagent. The tubes can be in subsurface contact with soil, including groundwater, and can be placed with directional drilling equipment independent of groundwater well casings. The soil-modifying reagent includes a variety of gases, liquids, colloids, and adsorbents that may be reactive or non-reactive with soil components. The method may be used inter alia to form reactive barriers, control pests, and enhance soil nutrients for microbes and plants.

  14. High-pressure soot formation and diffusion flame extinction characteristics of gaseous and liquid fuels

    NASA Astrophysics Data System (ADS)

    Karatas, Ahmet Emre

    High-pressure soot formation and flame stability characteristics were studied experimentally in laminar diffusion flames. For the former, radially resolved soot volume fraction and temperature profiles were measured in axisymmetric co-flow laminar diffusion flames of pre-vaporized n-heptane-air, undiluted ethylene-air, and nitrogen and carbon dioxide diluted ethylene-air at elevated pressures. Abel inversion was used to re-construct radially resolved data from the line-of-sight spectral soot emission measurements. For the latter, flame extinction strain rate was measured in counterflow laminar diffusion flames of C1-4 alcohols and hydrocarbon fuels of n-heptane, n-octane, iso-octane, toluene, Jet-A, and biodiesel. The luminous flame height, as marked by visible soot radiation, of the nitrogen- and helium-diluted n-heptane and nitrogen- and carbon dioxide-diluted ethylene flames stayed constant at all pressures. In pure ethylene flames, flame heights initially increased with pressure, but changed little above 5 atm. The maximum soot yield as a function of pressure in nitrogen-diluted n-heptane diffusion flames indicate that n-heptane flames are slightly more sensitive to pressure than gaseous alkane hydrocarbon flames at least up to 7 atm. Ethylene's maximum soot volume fractions were much higher than those of ethane and n-heptane diluted with nitrogen (fuel to nitrogen mass flow ratio is about 0.5). Pressure dependence of the peak carbon conversion to soot, defined as the percentage of fuel's carbon content converted to soot, was assessed and compared to previous measurements with other gaseous fuels. Maximum soot volume fractions were consistently lower in carbon dioxide-diluted flames between 5 and 15 atm but approached similar values to those in nitrogen-diluted flames at 20 atm. This observation implies that the chemical soot suppression effect of carbon dioxide, previously demonstrated at atmospheric pressure, is also present at elevated pressures up to 15 atm

  15. A comparison study of ash formation during pilot-scale combustion of pulverized coal and coal-water slurry fuels

    SciTech Connect

    Miller, S.F.

    1992-01-01

    The objective of this study was to investigate the effect of fuel form. specifically pulverized coal and coal-water slurry fuel (CWSF), on the particle size distribution (PSD) and inorganic composition of the ash formed during combustion. Three areas of primary interest were fuel particle and droplet size distribution, mineral matter PSD, and the composition and occurrence of inorganics in the fuel. The reactions of pyrite, silicates, aluminosilicates, and alkali and alkaline earth elements during combustion are traced. Two coals, a West Virginia Elk Creek high volatile A bituminous coal and the North Dakota Beulah lignite, were fired as a standard utility grind pulverized fuel and a CWSF at 316.2 MJ/h at 20% excess air in the Penn State Combustion Laboratory down-fired combustor. Fuel PSD and droplet size distribution of the pulverized coal and CWSF are important in determining the PSD of the respective ash when the PSD of the mineral matter and the composition and occurrence of the inorganics in the two fuels are similar, as in the case of the Elk Creek fuels. The mechanism for ash formation in both Elk Creek fuels was coalescence and agglomeration of the inorganics in the coal. The Elk Creek CWSF ash was coarser than the pulverized coal ash due to the larger CWSF char size formed during atomization. The average diameter of the inorganic particles identified in the pulverized coal ash was 2.6 times smaller than those identified in the fuel. The mechanism for ash formation in the Beulah CWSF was coalescence and agglomeration of inherent mineral matter. The average diameter of the inorganic particles identified in the CWSF ash was 3.3 times larger than those identified in the fuel.

  16. Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.

    SciTech Connect

    Hornstein, B. J.; Dattelbaum, D. M.; Schoonover, J. R.; Meyer, T. J.

    2004-01-01

    Ruthenium polypyridyl oxalate complexes are precursors to high oxidation state species that can catalyze the oxidation of a variety of substrates. Covalent attachment of these reactive species to surfaces such at ZrO{sub 2} or TiO{sub 2} inhibit catalyst deactivation and provide supports from which to build electrocatalytic and photoelectrocatalytic devices. Unfortunately, few details of the effects of surface binding on reactivity are available in the literature. To this end, precursors such as, Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4})(H{sub 2}O) and (C{sub 2}O{sub 4})(H{sub 2}O{sub 3}Ptpy)Ru-O-Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4}) (tpy is terpyridine) have been synthesized and attached to TiO{sub 2}. Quantitative surface binding studies were carried out and acid catalyzed solvolysis was used to form the aqua species. The complexes were oxidized with Ce(IV) to their high-valent analogs and their reactivity toward selected substrates was tested. These studies not only provide information about the effects of surface binding on the reactivity of metal oxides but also have implications for the development of light-driven catalysts.

  17. MODELING THE ATMOSPHERE FORMATION OF REACTIVE MERCURY IN FLORIDA AND THE GREAT LAKES

    EPA Science Inventory

    Reactive mercury in the troposphere is affected by a complex mix of local emissions, global-scale transport, and gas and aqueous-phase chemistry. Here, we describe a modified version of the EPA model for urban/regional air quality (CMAQ) to include the chemistry of mercury, and m...

  18. Reactivity and isotopic composition of spent PWR (pressurized-water-reactor) fuel as a function of initial enrichment, burnup, and cooling time

    SciTech Connect

    Cerne, S.P.; Hermann, O.W.; Westfall, R.M.

    1987-10-01

    This study presents the reactivity loss of spent PWR fuel due to burnup in terms of the infinite lattice multiplications factor, k/sub infinity/. Calculations were performed using the SAS2 and CSAS1 control modules of the SCALE system. The k/sub infinity/ values calculated for all combinations of six enrichments, seven burnups, and five cooling times. The results are presented as a primary function of enrichment in both tabular and graphic form. An equation has been developed to estimate the tabulated values of k/sub infinity/'s by specifying enrichment, cooling time, and burnup. Atom densities for fresh fuel, and spent fuel at cooling times of 2, 10, and 20 years are included. 13 refs., 8 figs., 8 tabs.

  19. Ice formation in PEM fuel cells operated isothermally at sub-freezing temperatures

    SciTech Connect

    Mukundan, Rangachary; Luhan, Roger W; Davey, John R; Spendelow, Jacob S; Borup, Rodney L; Hussey, Daniel S; Jacobson, David L; Arif, Muhammad

    2009-01-01

    The effect of MEA and GDL structure and composition on the performance of single-PEM fuel cells operated isothermally at subfreezing temperatures is presented. The cell performance and durability are not only dependent on the MEA/GDL materials used but also on their interfaces. When a cell is operated isothermally at sub-freezing temperatures in constant current mode, the water formation due to the current density initially hydrates the membrane/ionomer and then forms ice in the catalyst layer/GDL. An increase in high frequency resistance was also observed in certain MEAs where there is a possibility of ice formation between the catalyst layer and GDL leading to a loss in contact area. The total water/ice holding capacity for any MEA was lower at lower temperatures and higher current densities. The durability of MEAs subjected to multiple isothermal starts was better for LANL prepared MEAs as compared to commercial MEAs, and cloth GDLs when compared to paper GDLs. The ice formation was monitored using high-resolution neutron radiography and was found to be concentrated near the cathode catalyst layer. However, there was significant ice formation in the GDLs especially at the higher temperature ({approx} -10 C) and lower current density (0.02 A/cm{sup 2}) operations. These results are consistent with the longer-term durability observations that show more severe degradation at the lower temperatures.

  20. Fuel injector utilizing non-thermal plasma activation

    DOEpatents

    Coates, Don M.; Rosocha, Louis A.

    2009-12-01

    A non-thermal plasma assisted combustion fuel injector that uses an inner and outer electrode to create an electric field from a high voltage power supply. A dielectric material is operatively disposed between the two electrodes to prevent arcing and to promote the formation of a non-thermal plasma. A fuel injector, which converts a liquid fuel into a dispersed mist, vapor, or aerosolized fuel, injects into the non-thermal plasma generating energetic electrons and other highly reactive chemical species.

  1. Aging might augment reactive oxygen species (ROS) formation and affect reactive nitrogen species (RNS) level after myocardial ischemia/reperfusion in both humans and rats.

    PubMed

    Fan, Qian; Chen, Mulei; Fang, Xiangyang; Lau, Wayne Bond; Xue, Lei; Zhao, Lina; Zhang, Hui; Liang, Yan-Hong; Bai, Xi; Niu, Hong-Yu; Ye, Jing; Chen, Qing; Yang, Xinchun; Liu, Miaobing

    2013-08-01

    Previous studies indicate aging results in significantly decreased cardiac function and increased myocardial apoptosis after myocardial ischemia/reperfusion (MI/R) in humans or rats. The underlying mechanisms of aging-exacerbated effects remain unknown. Reactive oxygen species (ROS) and reactive nitrogen species (RNS) are known to play vital roles in aging-related MI/R injury. Heretofore, the effects of aging upon ROS and RNS formation were not investigated in humans, which is the focus of the current study. Due to experimental limitations with clinical trials, an additional animal experiment was performed. All enrolled acute myocardial infarction (AMI) patients received percutaneous coronary intervention (PCI) therapy. AMI patients were assigned into two groups: adult (age <65, n = 34) and elderly (age ≥65, n = 45) AMI patients. Blood samples were obtained from all study participants at 24 h and 3 days post-PCI. Plasma/white blood cell (WBC) ROS and RNS markers (malondialdehyde (MDA), myeloperoxidase (MPO), reduced glutathione (GSH), inducible nitric oxide synthase (iNOS) activity, NOx, and nitrotyrosine) were determined. The same markers were determined in rat cardiac tissue after 24 h MI/R. Compared to the adult group, elderly patients manifested increased plasma MDA and MPO and decreased plasma GSH concentrations. No significant differences in plasma NOx or nitrotyrosine concentration existed between adult and elderly patients. Furthermore, WBC iNOS activity in elderly patients was significantly decreased compared to the adult group. The measurement of ROS markers in the rat experiments was consistent and supported human study data. Surprisingly, RNS markers (NOx and nitrotyrosine) in blood and heart tissue increased from young to middle-aged rats but decreased from middle age to old age. Aging augments ROS, which might exacerbate MI/R injury. Additionally, our data support aging-induced changes of RNS levels in humans and rats in vivo.

  2. Experimental and Numerical Studies for Soot Formation in Laminar Coflow Diffusion Flames of Jet A-1 and Synthetic Jet Fuels

    NASA Astrophysics Data System (ADS)

    Saffaripour, Meghdad

    In the present doctoral thesis, fundamental experimental and numerical studies are conducted for the laminar, atmospheric pressure, sooting, coflow diffusion flames of Jet A-1 and synthetic jet fuels. The first part of this thesis presents a comparative experimental study for Jet A-1, which is a widely used petroleum-based fuel, and four synthetically produced alternative jet fuels. The main goals of this part of the thesis are to compare the soot emission levels of the alternative fuels to those of a standard fuel, Jet A-1, and to determine the effect of fuel chemical composition on soot formation characteristics. To achieve these goals, experimental measurements are constructed and performed for flame temperature, soot concentration, soot particle size, and soot aggregate structure in the flames of pre-vaporized jet fuels. The results show that a considerable reduction in soot production, compared to the standard fuel, can be obtained by using synthetic fuels which will help in addressing future regulations. A strong correlation between the aromatic content of the fuels and the soot concentration levels in the flames is observed. The second part of this thesis presents the development and experimental validation of a fully-coupled soot formation model for laminar coflow jet fuel diffusion flames. The model is coupled to a detailed kinetic mechanism to predict the chemical structure of the flames and soot precursor concentrations. This model also provides information on size and morphology of soot particles. The flames of a three-component surrogate for Jet A-1, a three-component surrogate for a synthetic jet fuel, and pure n-decane are simulated using this model. Concentrations of major gaseous species and flame temperatures are well predicted by the model. Soot volume fractions are predicted reasonably well everywhere in the flame, except near the flame centerline where soot concentrations are underpredicted by a factor of up to five. There is an excellent

  3. Evaluating temperature and fuel stratification for heat-release rate control in a reactivity-controlled compression-ignition engine using optical diagnostics and chemical kinetics modeling

    DOE PAGES

    Musculus, Mark P. B.; Kokjohn, Sage L.; Reitz, Rolf D.

    2015-04-23

    We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injectionmore » strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still

  4. An Atmospheric Pressure Plasma Setup to Investigate the Reactive Species Formation.

    PubMed

    Gorbanev, Yury; Soriano, Robert; O'Connell, Deborah; Chechik, Victor

    2016-11-03

    Non-thermal atmospheric pressure ('cold') plasmas have received increased attention in recent years due to their significant biomedical potential. The reactions of cold plasma with the surrounding atmosphere yield a variety of reactive species, which can define its effectiveness. While efficient development of cold plasma therapy requires kinetic models, model benchmarking needs empirical data. Experimental studies of the source of reactive species detected in aqueous solutions exposed to plasma are still scarce. Biomedical plasma is often operated with He or Ar feed gas, and a specific interest lies in investigation of the reactive species generated by plasma with various gas admixtures (O2, N2, air, H2O vapor, etc.) Such investigations are very complex due to difficulties in controlling the ambient atmosphere in contact with the plasma effluent. In this work, we addressed common issues of 'high' voltage kHz frequency driven plasma jet experimental studies. A reactor was developed allowing the exclusion of ambient atmosphere from the plasma-liquid system. The system thus comprised the feed gas with admixtures and the components of the liquid sample. This controlled atmosphere allowed the investigation of the source of the reactive oxygen species induced in aqueous solutions by He-water vapor plasma. The use of isotopically labelled water allowed distinguishing between the species originating in the gas phase and those formed in the liquid. The plasma equipment was contained inside a Faraday cage to eliminate possible influence of any external field. The setup is versatile and can aid in further understanding the cold plasma-liquid interactions chemistry.

  5. An Atmospheric Pressure Plasma Setup to Investigate the Reactive Species Formation

    PubMed Central

    Gorbanev, Yury; Soriano, Robert; O'Connell, Deborah; Chechik, Victor

    2016-01-01

    Non-thermal atmospheric pressure ('cold') plasmas have received increased attention in recent years due to their significant biomedical potential. The reactions of cold plasma with the surrounding atmosphere yield a variety of reactive species, which can define its effectiveness. While efficient development of cold plasma therapy requires kinetic models, model benchmarking needs empirical data. Experimental studies of the source of reactive species detected in aqueous solutions exposed to plasma are still scarce. Biomedical plasma is often operated with He or Ar feed gas, and a specific interest lies in investigation of the reactive species generated by plasma with various gas admixtures (O2, N2, air, H2O vapor, etc.) Such investigations are very complex due to difficulties in controlling the ambient atmosphere in contact with the plasma effluent. In this work, we addressed common issues of 'high' voltage kHz frequency driven plasma jet experimental studies. A reactor was developed allowing the exclusion of ambient atmosphere from the plasma-liquid system. The system thus comprised the feed gas with admixtures and the components of the liquid sample. This controlled atmosphere allowed the investigation of the source of the reactive oxygen species induced in aqueous solutions by He-water vapor plasma. The use of isotopically labelled water allowed distinguishing between the species originating in the gas phase and those formed in the liquid. The plasma equipment was contained inside a Faraday cage to eliminate possible influence of any external field. The setup is versatile and can aid in further understanding the cold plasma-liquid interactions chemistry. PMID:27842375

  6. Computational assessment of non-heteroatom-stabilized carbene complexes reactivity: formation of oxazine derivatives.

    PubMed

    Funes-Ardoiz, Ignacio; Sampedro, Diego

    2014-12-05

    A complete DFT-level mechanism elucidation of the two-step reaction of non-heteroatom-stabilized carbenes with imines, followed by addition of alkynes to yield oxazine derivatives, is presented. These compounds show different reactivity than the equivalent Fischer carbene complexes. A rationale of the experimental outcome is presented together with some suggestion for increasing the scope of the reaction, with special attention to the solvent effects in the regioselectivity.

  7. PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode

    NASA Astrophysics Data System (ADS)

    Tang, Hao; Qi, Zhigang; Ramani, Manikandan; Elter, John F.

    The impacts of unprotected start up and shut down on fuel cell performance degradation was investigated using both single cell and dual cell configurations. It was found that the air/fuel boundary developed at the anode side after a fuel cell shut down or during its restart caused extremely quick degradation of the cathode. The thickness, the electrochemical active surface area, and the performance of the cathode catalyst layer were significantly reduced. By using a dual cell configuration, cathode potential as high as two times of open circuit voltage was measured, and the corrosion current flowing externally between the two cells was detected and quantified. Carbon catalyst-support corrosion/oxidation at such a high potential was largely responsible for the accelerated fuel cell performance degradation.

  8. Some properties of the reactive hydroxylysyl residues in collagen: their possible role in nucleation during fibril formation.

    PubMed

    Gonzalez, E; Hamabata, A; Rojkind, M

    1984-10-01

    Native or heat-denatured collagens were incubated under controlled conditions of temperature and pH with variable molar ratios of KCNO or 2,4,6-trinitrobenzene sulphonic acid. The results obtained suggest that a small number of free amino groups are available for reaction on the native protein, while all the free amino groups react on the denatured protein. The highly reactive free amino groups in the native protein are hydroxylysine residues and have an abnormally low pK of 8.5 which is conformation dependent; this pK becomes normalized upon denaturation of the protein. The reactive hydroxylysines appear to be located in basic regions that could be the nucleation sites needed for fiber formation in the heat-gelation assay; the modified protein does not form stable fibrils upon heating at 37 degrees C and the few fibers formed are not stabilized after reduction with NaBH4. Our results also suggest that the triple helix in collagen is heterogeneous with respect to the reactivity of free amino groups and that several discrete transition temperatures are observed with two main breaks at 30 degrees C and at 37 degrees C, respectively.

  9. Development of a Mathematical Code to Predict Thermal Degradation of Fuel and Deposit Formation in a Fuel System

    DTIC Science & Technology

    1990-09-01

    MDTCAP 5,7 7 0A DCLML",," pROCESSING SHEIET srx is 5X.!iiACSTD AD- A225 415 WRDC-TR-90-2084 DEVELOPMENT OF A MATHEMATICAL CODE TO PREDICT THERMAL...R. (1983) "Studies of the Mechanism of Turbine Fuel Instability," Colorado School of Mines, NASA CR -167963. Daniel, S. R. (1985) "Jet Fuel Instability

  10. From the Nano- to the Formation Scale: Accessible Reactive Surface Area in a CO2 Saline Reservoir

    NASA Astrophysics Data System (ADS)

    Swift, A.; Cole, D. R.; Sheets, J. M.; Anovitz, L. M.

    2015-12-01

    Among the outstanding subsurface science challenges today is the translation of our improved understanding of pore-scale reactive transport and bench-scale geochemical rates of reaction to the prediction of long-term formation response to the sequestration of carbon dioxide. The emergent complexity of CO2-brine-rock interactions, on a large scale, over long periods of time (up to 1000 years) arises from a number of imperfectly understood factors. Of these, the accessibility of reactive surfaces distinguishes natural materials from powders commonly used in reaction rate studies, and geologic heterogeneity requires a workflow that connects samples, not to depths, but to material types that, combined, constitute a subsurface formation. To this end, core samples targeting every lithology type (quartz arenite, quartz-feldspar arenite, hematitic matrix-rich sandstone, clay-silt lens) observed in two bore holes through the Mt. Simon Sandstone of Ohio have been interrogated. Small- and ultra small-angle neutron scattering (SANS, USANS) and mercury and gas porosimetry (MICP, BET) have been used to quantify pore and pore throat distributions, and therefore pore volume accessibility at any given intrusion pressure. Mineral surface area is calculated using high-resolution SEM-BSE imagery combined with energy dispersive X-ray mineral mapping, and then extended beyond the limit of image-based techniques by using BET estimates for specific minerals. Combined, these datasets enable the quantification of mineral-specific, connected surface area as a function of pore/fracture scale. This is a defining feature of a pore-mineral assemblage, the microanalysis analogue of a macroscale lithology. The whole formation is then reconstructed by connecting pore-mineral assemblages to lithologies, defined by permeability/porosity and by mineralogy, and these in turn to the whole vertical extent of the formation using coarser-scale images of whole core. This effort therefore contributes both to

  11. Measurement of the atmospheric reactivity of emissions from gasoline and alternative-fueled vehicles: Assessment of available methodologies. Part 1. Indoor smog chamber study of reactivity. Part 2. Assessment of airtrak as a reactivity analyzer. Final report for the second year, March 1, 1994-February 28, 1995

    SciTech Connect

    Kelly, N.A.; Wang, P.; Hurley, M.D.; Japar, S.M.; Chang, T.

    1996-06-13

    During the second year of the GM smog chamber study of incremental reactivity the authors performed smog chamber experiments to measure three important properties of incremental reactivity. First, they challenged the linear relationship between the Carter factors and the chamber-measured reactivities found during the first-year smog chamber study. Second, they compared the predicted and measured smog formation in simple and complex mixtures. Third, they measured the incremental reactivities of three hydrocarbons (n-butane, propene, and p-xylene) as well as the urban-surrogate mixture at three different temperatures, 22 deg C, 32 deg C (the default), and 42 deg C, to determine how temperature affects both the absolute and the relative reactivity. Finally, they conducted experiments in which the incremental reactivity of NO2 was measured in order to test the Integrated Empirical Rate (IER) model.

  12. Potential for Peroxide and Gum Formation in Ultra-Low-Sulfur Diesel Fuels

    DTIC Science & Technology

    2007-10-31

    Study of the Thermal Decomposition of Cumene Hydroperoxide and Fuel Instability Reactions , Energy & Fuels, 1994, 8, 851. 3. Fodor, G. E.; Naegeli...the fuel. These chemical processes can lead to changes in color; the development of insoluble reaction products, including soluble and adherent gums...fuels. The LPR test uses elevated temperatures (100 oC) and air overpressures (50 psi) to increase the rate of oxidation reactions in the fuel. The

  13. Formation of cubic boron-nitride by the reactive sputter deposition of boron

    SciTech Connect

    Jankowski, A.F.; Hayes, J.P.; Makowiecki, D.W.; McKeman, M.A.

    1997-03-01

    Boron-nitride films are synthesized by RF magnetron sputtering boron targets where the deposition parameters of gas pressure, flow and composition are varied along with substrate temperature and applied bias. The films are analyzed using Auger electron spectroscopy, transmission electron microscopy, nanoindentation, Raman spectroscopy and x-ray absorption spectroscopy. These techniques provide characterization of film composition, crystalline structure, hardness and chemical bonding, respectively. Reactive, rf-sputtering process parameters are established which lead to the growth of crystalline BN phases. The deposition of stable and adherent boron nitride coatings consisting of the cubic phase requires 400 `C substrate heating and the application of a 300 V negative bias.

  14. Chemical reactivity parameters (HSAB) applied to magma evolution and ore formation

    NASA Astrophysics Data System (ADS)

    Vigneresse, Jean-Louis

    2012-11-01

    Magmas are commonly described through the usual content of 10 major oxides. This requires a complex dimensional plot. Concepts of hard-soft acid-base (HSAB) interactions allow estimating chemical reactivity of elements, such as electronegativity, i.e. the chemical potential changed of sign, hardness and electrophilicity. For complex system, those values result from equalization methods, i.e. the equalization of the respective chemical potentials, or from ab-initio computations through density functional theory (DFT). They help to characterize silicate magmas by a single value describing their reactivity. Principles of minimum electrophilicity (mEP), maximum hardness (MHP) and minimum polarizability (mPP) indicate trends towards regions of higher stability. Those parameters are plotted within a fitness landscape diagram, highlighting toward which principle reactions trend. Major oxides, main minerals and magmas determine the respective fields in which evolve natural rocks. Three poles are identified, represented by silica and alkalis, whereas oxidation forms the third trend. Mantle-derived rocks show a large variation in electrophilicity compared to hardness. They present all characters of a closed chemical system, being simply described by the free Gibbs energy. Conversely, rocks contaminated within the continental crust show a large variation in hardness between a silica pole and an alkaline, defining two separate trends. The trends show the character of an open chemical system, requiring a Grand Potential description (i.e. taking into account the difference in chemical potential). The terms open and closed systems refer to thermodynamical description, implying contamination for the crust and recycling for the mantle. The specific role of alkalis contrasts with other cations, pointing to their behavior in modifying silicate polymer structures. A second application deals with the reactivity of the melt and its fluid phase. It leads to a better understanding on the

  15. Evaluation of a High-Throughput Peptide Reactivity Format Assay for Assessment of the Skin Sensitization Potential of Chemicals

    PubMed Central

    Wong, Chin Lin; Lam, Ai-Leen; Smith, Maree T.; Ghassabian, Sussan

    2016-01-01

    The direct peptide reactivity assay (DPRA) is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate, and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium, and high concentrations) and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme, and non-sensitizers) with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF), cysteine- (Ac-RFAACAA), and lysine- (Ac-RFAAKAA) containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7%) and glass (47.3%) vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2, 4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further highlight

  16. Evaluation of a High-Throughput Peptide Reactivity Format Assay for Assessment of the Skin Sensitization Potential of Chemicals.

    PubMed

    Wong, Chin Lin; Lam, Ai-Leen; Smith, Maree T; Ghassabian, Sussan

    2016-01-01

    The direct peptide reactivity assay (DPRA) is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate, and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium, and high concentrations) and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme, and non-sensitizers) with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF), cysteine- (Ac-RFAACAA), and lysine- (Ac-RFAAKAA) containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7%) and glass (47.3%) vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2, 4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further highlight

  17. Formation, Reactivity, and Properties of Nondative Late Transition Metal–Oxygen and–Nitrogen Bonds

    PubMed Central

    FULTON, J. ROBIN; HOLLAND, ANDREW W.; FOX, DANIEL J.; BERGMAN*, ROBERT G.

    2005-01-01

    Complexes containing bonds between heteroatoms such as nitrogen and oxygen and “late” transition metals (i.e., those located on the right side of the transition series) have been implicated as reactive intermediates in numerous important catalytic systems. Despite this, our understanding of such M–X linkages still lags behind that of their M–H and M–C analogues. New synthetic strategies have now made possible the isolation and study of a variety of monomeric late-metal alkoxide, aryloxide, and amide complexes, including parent hydroxide and amide species. The heteroatoms in these materials form surprisingly strong bonds to their metal centers, and their bond energies do not necessarily correlate with the energies of the corresponding H–X bonds. The M–X complexes typically exhibit nucleophilic reactivity, in some cases form strong hydrogen bonds to proton donors, and even deprotonate relatively weak acids. These observations, as well as thermodynamic investigations, suggest that late metal–heteroatom bonds are strongly polarized and possess significant ionic character, properties that play an important role in their interactions with organic compounds. PMID:11790088

  18. Film formation from aqueous polyurethane dispersions of reactive hydrophobic and hydrophilic components; spectroscopic studies and Monte Carlo simulations.

    PubMed

    Otts, Daniel B; Cueva-Parra, Luis A; Pandey, Ras B; Urban, Marek W

    2005-04-26

    Film formation of waterborne two-component polyurethanes is exceedingly complex due to the heterogeneous nature along with simultaneous progression of several parallel physicochemical processes which include water evaporation, cross-linking reactions, phase separation, and droplet coalescence, to name a few. While internal reflection infrared imaging (IRIRI) spectroscopy clearly facilitates analysis of chemical changes resulting from film formation, the complexity of processes leading to formation of specific surface/interfacial entities is a major experimental challenge. For this reason, we combined a spectrum of surface/interfacial analytical approaches including IRIRI, atomic force microscopy, and attenuated total reflectance Fourier transform infrared spectroscopy with Monte Carlo computer simulations to advance the limited knowledge of how temperature, stoichiometry, concentration levels, and reactivities of individual components affect the development of surface morphologies and compositional gradients across the film thickness. These studies show that in heterogeneous systems having both hydrophobic and hydrophilic components stratification of individual components to the film-air (F-A) interface is ultimately responsible for formation of rough surface topographies. These studies show that simultaneous stratification of hydrophobic components along with water evaporation to the F-A interface results in metastable interfacial layers, leading to surface dewetting. Subsequently, surface roughness is enhanced by higher concentrations of water in the cross-linking film.

  19. Blue-light dependent reactive oxygen species formation by Arabidopsis cryptochrome may define a novel evolutionarily conserved signaling mechanism.

    PubMed

    Consentino, Laurent; Lambert, Stefan; Martino, Carlos; Jourdan, Nathalie; Bouchet, Pierre-Etienne; Witczak, Jacques; Castello, Pablo; El-Esawi, Mohamed; Corbineau, Francoise; d'Harlingue, Alain; Ahmad, Margaret

    2015-06-01

    Cryptochromes are widespread blue-light absorbing flavoproteins with important signaling roles. In plants they mediate de-etiolation, developmental and stress responses resulting from interaction with downstream signaling partners such as transcription factors and components of the proteasome. Recently, it has been shown that Arabidopsis cry1 activation by blue light also results in direct enzymatic conversion of molecular oxygen (O2 ) to reactive oxygen species (ROS) and hydrogen peroxide (H2 O2 ) in vitro. Here we explored whether direct enzymatic synthesis of ROS by Arabidopsis cry1 can play a physiological role in vivo. ROS formation resulting from cry1 expression was measured by fluorescence assay in insect cell cultures and in Arabidopsis protoplasts from cryptochrome mutant seedlings. Cell death was determined by colorimetric assay. We found that ROS formation results from cry1 activation and induces cell death in insect cell cultures. In plant protoplasts, cryptochrome activation results in rapid increase in ROS formation and cell death. We conclude that ROS formation by cryptochromes may indeed be of physiological relevance and could represent a novel paradigm for cryptochrome signaling.

  20. Asbestos inhalation induces reactive nitrogen species and nitrotyrosine formation in the lungs and pleura of the rat.

    PubMed Central

    Tanaka, S; Choe, N; Hemenway, D R; Zhu, S; Matalon, S; Kagan, E

    1998-01-01

    To determine whether asbestos inhalation induces the formation of reactive nitrogen species, three groups of rats were exposed intermittently over 2 wk to either filtered room air (sham-exposed) or to chrysotile or crocidolite asbestos fibers. The rats were killed at 1 or 6 wk after exposure. At 1 wk, significantly greater numbers of alveolar and pleural macrophages from asbestos-exposed rats than from sham-exposed rats demonstrated inducible nitric oxide synthase protein immunoreactivity. Alveolar macrophages from asbestos-exposed rats also generated significantly greater nitrite formation than did macrophages from sham-exposed rats. Strong immunoreactivity for nitrotyrosine, a marker of peroxynitrite formation, was evident in lungs from chrysotile- and crocidolite-exposed rats at 1 and 6 wk. Staining was most evident at alveolar duct bifurcations and within bronchiolar epithelium, alveolar macrophages, and the visceral and parietal pleural mesothelium. Lungs from sham-exposed rats demonstrated minimal immunoreactivity for nitrotyrosine. Significantly greater quantities of nitrotyrosine were detected by ELISA in lung extracts from asbestos-exposed rats than from sham-exposed rats. These findings suggest that asbestos inhalation can induce inducible nitric oxide synthase activation and peroxynitrite formation in vivo, and provide evidence of a possible alternative mechanism of asbestos-induced injury to that thought to be induced by Fenton reactions. PMID:9664087

  1. Fundamental Studies of Irradiation-Induced Defect Formation and Fission Product Dynamics in Oxide Fuels

    SciTech Connect

    Stubbins, James

    2012-12-19

    The objective of this research program is to address major nuclear fuels performance issues for the design and use of oxide-type fuels in the current and advanced nuclear reactor applications. Fuel performance is a major issue for extending fuel burn-up which has the added advantage of reducing the used fuel waste stream. It will also be a significant issue with respect to developing advanced fuel cycle processes where it may be possible to incorporate minor actinides in various fuel forms so that they can be 'burned' rather than join the used fuel waste stream. The potential to fission or transmute minor actinides and certain long-lived fission product isotopes would transform the high level waste storage strategy by removing the need to consider fuel storage on the millennium time scale.

  2. Formation mechanism of gas bubble superlattice in UMo metal fuels: Phase-field modeling investigation

    NASA Astrophysics Data System (ADS)

    Hu, Shenyang; Burkes, Douglas E.; Lavender, Curt A.; Senor, David J.; Setyawan, Wahyu; Xu, Zhijie

    2016-10-01

    Nano-gas bubble superlattices are often observed in irradiated UMo nuclear fuels. However, the formation mechanism of gas bubble superlattices is not well understood. A number of physical processes may affect the gas bubble nucleation and growth; hence, the morphology of gas bubble microstructures including size and spatial distributions. In this work, a phase-field model integrating a first-passage Monte Carlo method to investigate the formation mechanism of gas bubble superlattices was developed. Six physical processes are taken into account in the model: 1) heterogeneous generation of gas atoms, vacancies, and interstitials informed from atomistic simulations; 2) one-dimensional (1-D) migration of interstitials; 3) irradiation-induced dissolution of gas atoms; 4) recombination between vacancies and interstitials; 5) elastic interaction; and 6) heterogeneous nucleation of gas bubbles. We found that the elastic interaction doesn't cause the gas bubble alignment, and fast 1-D migration of interstitials along <110> directions in the body-centered cubic U matrix causes the gas bubble alignment along <110> directions. It implies that 1-D interstitial migration along [110] direction should be the primary mechanism of a fcc gas bubble superlattice which is observed in bcc UMo alloys. Simulations also show that fission rates, saturated gas concentration, and elastic interaction all affect the morphology of gas bubble microstructures.

  3. Relaxing the formation of hypoxic bottom water with sediment microbial fuel cells.

    PubMed

    Touch, Narong; Hibino, Tadashi; Morimoto, Yuki; Kinjo, Nobutaka

    2017-02-08

    The method of improving bottom water environment using industrial wastes to suppress diffusion substances from bottom sediment has recently captured the attention of many researchers. In this study, wastewater discharge-derived sediment was used to examine an alternative approach involving the use of sediment microbial fuel cells (SMFCs) in relaxing the formation of hypoxic bottom water, and removing reduced substances from sediment. Concentrations of dissolved oxygen (DO) and other ions were measured in overlying water and sediment pore water with and without the application of SMFCs. The results suggest that SMFCs can markedly reduce hydrogen sulfide and manganese ion concentrations in overlying water, and decrease the depletions of redox potential and DO concentration. In addition, SMFCs can dissolve ferric compounds in the sediment and thereby release the ferric ion available to fix phosphate in the sediment. Our results indicate that SMFCs can be used as an alternative method to relax the formation of hypoxic bottom water and to remove reduced substances from the sediment, thus improving the quality of both water and sediment environments.

  4. In Situ Imaging of Particle Formation and Dynamics in Reactive Material Deflagrations

    SciTech Connect

    Sullivan, Kyle T.

    2016-12-12

    Reactive composites utilizing nanoparticles have been the topic of extensive research in the past two decades. The driver for this is that, as the particle size is decreased, the mixing scale between constituents is greatly reduced, which has long thought to increase the rate of chemical reaction. While a general trend of increased reactivity has been seen for metal / metal oxide, or thermite, reactive materials, some results have demonstrated diminishing returns as the particle size is further decreased. Recent results have shown that nanoparticles, which are typically aggregates of several primary particles, can undergo very rapid coalescence to form micron particles once a critical temperature is reached. Experiments on this topic to date have been performed on very small sample masses, and sometimes under vacuum; conditions which are not representative of the environment during a deflagration. In this feasibility study, a custom burn tube was used to ignite and react 100 mg powdered thermite samples in long acrylic tubes. X-ray imaging at APS Sector 32 was performed to image the particle field as a function of distance and time as the rarefied particle cloud expanded and flowed down the tube. Five different thermite formulations were investigated, Al / CuO, Al / Fe2O3, Al / SnO2, Al / WO3, and Al / Fe2O3, along with Al / CuO formulations with different sizes of Al particles ranging from 80 nm to approximate 10 μm. The results clearly show that the sample powder reacts and unloads into a distribution of larger micron-scale particles (~5-500 μm), which continue to react and propagate as the particle-laden stream flows down the tube. This was the first direct imaging of the particle field during a thermite deflagration, and gives significant insight into the evolution of reactants to products. Analysis of phase is currently being pursued to determine whether this method can be used to extract

  5. Shock tube study of the fuel molecular structure effects on the chemical kinetic mechanisms for soot formation

    NASA Technical Reports Server (NTRS)

    Krech, R. H.; Cowles, L. M.; Rawlins, W. T.

    1983-01-01

    The objective of this research effort is to investigate the gas-phase mechanisms which lead to soot formation in the combustion of complex hydrocarbon fuels. The fuel decomposition is studied under pyrolytic and oxidative conditions behind incident shock waves, using various optical diagnostics to monitor particle appearance and the behavior of gas phase species. In particular, we are investigating: (1) improved quantification of UV/visible soot yield measurements using infrared attenuation and emission techniques; (2) spectral characteristics of gas-phase emission and absorption in the ultraviolet, visible, and infrared; and (3) a conceptual view of the chemical pathways for fuel decomposition and the gas-phase reactions leading to soot formation.

  6. Microemulsions and Aggregation Formation in Extraction Processes for Used Nuclear Fuel: Thermodynamic and Structural Studies

    SciTech Connect

    Nilsson, Mikael

    2016-05-04

    Advanced nuclear fuel cycles rely on successful chemical separation of various elements in the used fuel. Numerous solvent extraction (SX) processes have been developed for the recovery and purification of metal ions from this used material. However, the predictability of process operations has been challenged by the lack of a fundamental understanding of the chemical interactions in several of these separation systems. For example, gaps in the thermodynamic description of the mechanism and the complexes formed will make predictions very challenging. Recent studies of certain extraction systems under development and a number of more established SX processes have suggested that aggregate formation in the organic phase results in a transformation of its selectivity and efficiency. Aggregation phenomena have consistently been interfering in SX process development, and have, over the years, become synonymous with an undesirable effect that must be prevented. This multiyear, multicollaborative research effort was carried out to study solvation and self-organization in non-aqueous solutions at conditions promoting aggregation phenomena. Our approach to this challenging topic was to investigate extraction systems comprising more than one extraction reagent where synergy of the metal ion could be observed. These systems were probed for the existence of stable microemulsions in the organic phase, and a number of high-end characterization tools were employed to elucidate the role of the aggregates in metal ion extraction. The ultimate goal was to find connections between synergy of metal ion extraction and reverse micellar formation. Our main accomplishment for this project was the expansion of the understanding of metal ion complexation in the extraction system combining tributyl phosphate (TBP) and dibutyl phosphoric acid (HDBP). We have found that for this system no direct correlation exists for the metal ion extraction and the formation of aggregates, meaning that the

  7. Characteristics of Reactive Ni3Sn4 Formation and Growth in Ni-Sn Interlayer Systems

    NASA Astrophysics Data System (ADS)

    Lis, Adrian; Kenel, Christoph; Leinenbach, Christian

    2016-06-01

    The near-isothermal growth and formation of Ni3Sn4 intermetallic compounds (IMC) in Ni-Sn interlayer systems was studied in the solid state at 473 K (200 °C) and under solid-liquid conditions at 523 and 573 K (250 °C and 300 °C) from an initial state of a few seconds. Scalloped solid-state IMC formation was mainly driven by grain boundary diffusion of Ni through the IMC layer combined with the grain coarsening of the IMC layer. Under solid-liquid conditions, the formation of faceted and needle-shaped Ni3Sn4 grains as well as an atypical IMC growth behavior with similar parabolic growth constants for 523 K and 573 K (250 °C and 300 °C) was observed within the first 180 seconds of the holding time, and IMC growth occurred as an isothermal solidification from the Ni-saturated Sn melt. Due to the progressive densification of the IMC layer and the diffusion-controlled growth, the kinetics slowed down by approximately one order of magnitude after 180 seconds of annealing. The final stage was characterized by the formation of IMC islands ahead of the interfacial Ni3Sn4 layer. Needle-like IMC growth was effectively suppressed under combined solid-state and solid-liquid conditions. Textured Ni3Sn4 IMC formation at the Ni-Sn interface was approved with pole figure measurements. The activation energy Q for solid-liquid IMC formation was calculated as 43.3 kJ/mol, and processing maps for IMC growth and Sn consumption were derived as functions of temperature and time, respectively.

  8. Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba)

    NASA Astrophysics Data System (ADS)

    Domènech, Cristina; Galí, Salvador; Villanova-de-Benavent, Cristina; Soler, Josep M.; Proenza, Joaquín A.

    2017-01-01

    Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 106 years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite. Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations.

  9. Formation of silicon nanostructures with a combination of spacer technology and deep reactive ion etching

    PubMed Central

    2012-01-01

    A new method of fabricating high aspect ratio nanostructures in silicon without the use of sub-micron lithographic technique is reported. The proposed method comprises two important steps including the use of CMOS spacer technique to form silicon nitride nanostructure masking followed by deep reactive ion etching (DRIE) of the silicon substrate to form the final silicon nanostructures. Silicon dioxide is used as the sacrificial layer to form the silicon nitride nanostructures. With DRIE a high etch selectivity of 50:1 between silicon and silicon nitride was achieved. The use of the spacer technique is particularly advantageous where self-aligned nanostructures with potentially unlimited lengths are formed without the need of submicron lithographic tools and resist materials. With this method, uniform arrays of 100 nm silicon nanostructures which are at least 4 μm tall with aspect ratio higher than 40 were successfully fabricated. PMID:22672745

  10. Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    1994-01-01

    Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

  11. Combustion of Various Highly Reactive Fuels in a 3.84- by 10-inch Mach 2 Wind Tunnel

    NASA Technical Reports Server (NTRS)

    Allen, Harrison, Jr.; Fletcher, Edward A.

    1959-01-01

    The following fuels and fuel combinations injected from the top wall of a Mach 2 wind tunnel were successfully burned and gave associated pressure rises: aluminum borohydride, pentaborane, mixtures containing up to 41 percent JP-4 fuel in aluminum borohydride, tandem injections of aluminum borohydride, tandem injections of JP-4 fuel and aluminum borohydride, trimethyl aluminum with water injections, and diethyl aluminum hydride with water injections. The following fuels could not be ignited at the tunnel conditions (static pressure, 5.6 in. Hg; static temperature, -148 F): trimethylborane, triethylborane, propylpentaborane, ethyl- decaborane, and vinylsilane. Studies in which the heated region was probed by water injections indicated that the flow downstream of the flame front is subsonic and recirculating.

  12. Contribution of energetically reactive surface features to the dissolution of CeO2 and ThO2 analogues for spent nuclear fuel microstructures.

    PubMed

    Corkhill, Claire L; Myllykylä, Emmi; Bailey, Daniel J; Thornber, Stephanie M; Qi, Jiahui; Maldonado, Pablo; Stennett, Martin C; Hamilton, Andrea; Hyatt, Neil C

    2014-08-13

    In the safety case for the geological disposal of nuclear waste, the release of radioactivity from the repository is controlled by the dissolution of the spent fuel in groundwater. There remain several uncertainties associated with understanding spent fuel dissolution, including the contribution of energetically reactive surface sites to the dissolution rate. In this study, we investigate how surface features influence the dissolution rate of synthetic CeO2 and ThO2, spent nuclear fuel analogues that approximate as closely as possible the microstructure characteristics of fuel-grade UO2 but are not sensitive to changes in oxidation state of the cation. The morphology of grain boundaries (natural features) and surface facets (specimen preparation-induced features) was investigated during dissolution. The effects of surface polishing on dissolution rate were also investigated. We show that preferential dissolution occurs at grain boundaries, resulting in grain boundary decohesion and enhanced dissolution rates. A strong crystallographic control was exerted, with high misorientation angle grain boundaries retreating more rapidly than those with low misorientation angles, which may be due to the accommodation of defects in the grain boundary structure. The data from these simplified analogue systems support the hypothesis that grain boundaries play a role in the so-called "instant release fraction" of spent fuel, and should be carefully considered, in conjunction with other chemical effects, in safety performance assessements for the geological disposal of spent fuel. Surface facets formed during the sample annealing process also exhibited a strong crystallographic control and were found to dissolve rapidly on initial contact with dissolution medium. Defects and strain induced during sample polishing caused an overestimation of the dissolution rate, by up to 3 orders of magnitude.

  13. Reactivity of Iron-bearing Minerals in Deep Saline Formations subjected to Carbon Injection

    NASA Astrophysics Data System (ADS)

    Schoonen, M. A.; Sklute, E. C.; Strongin, D. R.; Dyar, M. D.

    2013-12-01

    Deep saline aquifers are being considered as repositories for captured CO2. Here the influence of co-injected hydrogen sulfide and sulfur dioxide on the reactivity of hematite-bearing sandstones was evaluated as a function of salt content and water/rock ratio. The reactivity of the Triassic Moenkopi red sandstone under scCO2-dominated conditions (supercritical fluid around the point of injection) and water-dominated conditions (aqueous phase influenced by the injection of scCO2) was studied. Flow-through experiments were used to simulate scCO2-dominated conditions. Crushed sandstone packed in a column was exposed to a co-mingled stream of supercritical CO2 and an aqueous H2S or SO2 solution (75°C). Batch experiments to simulate water-dominated conditions were conducted in small autoclaves that were loaded with crushed sandstone, a small amount of water, and dry ice before to 75°C. The role of water/rock ratio was explored by conducting experiments at a water/rock ratio of 4.3/1 and 1.4/1. The reacted sandstones were recovered at the conclusion of each type of experiment and analyzed for changes in mineralogical composition using X-ray Diffraction. Selected reaction products were also studied using Mössbauer spectroscopy, FTIR, and Visible Near Infrared (VNIR) spectroscopy. The results of the flow through experiments, simulating scCO2-dominated conditions, showed no changes in the iron mineralogy of the sand, regardless of whether pure scCO2 or scCO2 co-mingled with SO2 or H2S was used. By contrast, batch experiments, simulating water-dominated conditions, showed significant changes in iron mineralogy. The presence of sulfide led to the conversion of the hematite component in the sandstone to pyrite at all salt concentrations (0-6M NaCl). In experiments with sulfide and sulfite, siderite and pyrite formed, but siderite was favored at higher salinity and lower water/rock ratio. Availability of water at the mineral surface might be a critical factor in the

  14. Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization.

    PubMed

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-02-21

    Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are

  15. Heat-induced formation of reactive oxygen species and 8-oxoguanine, a biomarker of damage to DNA

    PubMed Central

    Bruskov, Vadim I.; Malakhova, Lyudmila V.; Masalimov, Zhaksylyk K.; Chernikov, Anatoly V.

    2002-01-01

    Heat-induced formation of 8-oxoguanine was demonstrated in DNA solutions in 10–3 M phosphate buffer, pH 6.8, by enzyme-linked immunosorbent assays using monoclonal antibodies against 8-oxoguanine. A radiation-chemical yield of 3.7 × 10–2 µmol J–1 for 8-oxoguanine production in DNA upon γ-irradiation was used as an adequate standard for quantitation of 8-oxoguanine in whole DNA. The initial yield of heat-induced 8-oxoguanine exhibits first order kinetics. The rate constants for 8-oxoguanine formation were determined at elevated temperatures; the activation energy was found to be 27 ± 2 kcal/mol. Extrapolation to 37°C gave a value of k37 = 4.7 × 10–10 s–1. Heat-induced 8-oxoguanine formation and depurination of guanine and adenine show similarities of the processes, which implies that heat-mediated generation of reactive oxygen species (ROS) should occur. Heat-induced production of H2O2 in phosphate buffer was shown. The sequence of reactions of thermally mediated ROS formation have been established: activation of dissolved oxygen to the singlet state, generation of superoxide radicals and their dismutation to H2O2. Gas saturation (O2, N2 and Ar), D2O, scavengers of 1O2, O2–• and OH• radicals and metal chelators influenced heat-induced 8-oxoguanine formation as they affected thermal ROS generation. These findings imply that heat acts via ROS attack leading to oxidative damage to DNA. PMID:11884633

  16. Hematin−Hematin Self-Association States Involved in the Formation and Reactivity of the Malaria Parasite Pigment, Hemozoin

    SciTech Connect

    Klonis, Nectarios; Dilanian, Ruben; Hanssen, Eric; Darmanin, Connie; Streltsov, Victor; Deed, Samantha; Quiney, Harry; Tilley, Leann

    2010-10-22

    The malaria parasite pigment, hemozoin, is a crystal of ferriprotoporphyrin IX (FP-Fe(III)), a product of hemoglobin digestion. Hemozoin formation is essential for FP-Fe(III) detoxification in the parasite; it is the main target of quinoline antimalarials and can modulate immune and inflammation responses. To gain further insight into the likely mechanisms of crystal formation and hemozoin reactivity, we have reanalyzed the crystal structure data for {beta}-hematin and solved the crystal structure of Plasmodium falciparum hemozoin. The analysis reveals that the structures are very similar and highlights two previously unexplored modes of FP-Fe(III) self-association involving {pi}-{pi} interactions that may initiate crystal formation and help to stabilize the extended structure. Hemozoin can be considered to be a crystal composed of {pi}-{pi} dimers stabilized by iron-carboxylate linkages. As a result, it is predicted that two surfaces of the crystal would consist of {pi}-{pi} dimers with Fe(III) partly exposed to solvent and capable of undergoing redox reactions. Accordingly, we demonstrate that the crystal possesses both general peroxidase activity and the ability to cause lipid oxidation.

  17. Resveratrol inhibits foam cell formation via NADPH oxidase 1-mediated reactive oxygen species and monocyte chemotactic protein-1

    PubMed Central

    Park, Dae-Weon; Baek, Kheewoong; Kim, Jae-Ryong; Lee, Jae-Jin; Ryu, Sang-Ho; Chin, Byung-Rho

    2009-01-01

    Resveratrol is a polyphenolic compound in red wine that has anti-oxidant and cardioprotective effects in animal models. Reactive oxygen species (ROS) and monocyte chemotactic protein-1 (MCP-1) play key roles in foam cell formation and atherosclerosis. We studied LPS-mediated foam cell formation and the effect of resveratrol. Resveratrol pretreatment strongly suppressed LPS-induced foam cell formation. To determine if resveratrol affected the expression of genes that control ROS generation in macrophages, NADPH oxidase 1 (Nox1) was measured. Resveratrol treatment of macrophages inhibited LPS-induced Nox1 expression as well as ROS generation, and also suppressed LPS-induced MCP-1 mRNA and protein expression. We investigated the upstream targets of Nox1 and MCP-1 expression and found that Akt-forkhead transcription factors of the O class (FoxO3a) is an important signaling pathway that regulates both genes. These inhibitory effects of resveratrol on Nox1 expression and MCP-1 production may target to the Akt and FoxO3a signaling pathways. PMID:19293636

  18. Higher platelet reactivity and platelet-monocyte complex formation in Gram-positive sepsis compared to Gram-negative sepsis.

    PubMed

    Tunjungputri, Rahajeng N; van de Heijden, Wouter; Urbanus, Rolf T; de Groot, Philip G; van der Ven, Andre; de Mast, Quirijn

    2016-12-29

    Platelets may play a role in the high risk for vascular complications in Gram-positive sepsis. We compared the platelet reactivity of 15 patients with Gram-positive sepsis, 17 with Gram-negative sepsis and 20 healthy controls using a whole blood flow cytometry-based assay. Patients with Gram-positive sepsis had the highest median fluorescence intensity (MFI) of the platelet membrane expression of P-selectin upon stimulation with high dose adenosine diphosphate (ADP; P = 0.002 vs. Gram-negative and P = 0.005 vs. control groups) and cross-linked collagen-related peptide (CRP-XL; P = 0.02 vs. Gram-negative and P = 0.0001 vs. control groups). The Gram-positive group also demonstrated significantly higher ADP-induced fibrinogen binding (P = 0.001), as wll as platelet-monocyte complex formation (P = 0.02), compared to the Gram-negative group and had the highest plasma levels of platelet factor 4, β-thromboglobulin and soluble P-selectin. In contrast, thrombin-antithrombin complex and C-reactive protein levels were comparable in both patient groups. In conclusion, common Gram-positive pathogens induce platelet hyperreactivity, which may contribute to a higher risk for vascular complications.

  19. Cold stress increases reactive oxygen species formation via TRPA1 activation in A549 cells.

    PubMed

    Sun, Wenwu; Wang, Zhonghua; Cao, Jianping; Cui, Haiyang; Ma, Zhuang

    2016-03-01

    Reactive oxygen species (ROS) are responsible for lung damage during inhalation of cold air. However, the mechanism of the ROS production induced by cold stress in the lung is still unclear. In this work, we measured the changes of ROS and the cytosolic Ca(2+) concentration ([Ca(2+)]c) in A549 cell. We observed that cold stress (from 20 to 5 °C) exposure of A549 cell resulted in an increase of ROS and [Ca(2+)]c, which was completely attenuated by removing Ca(2+) from medium. Further experiments showed that cold-sensing transient receptor potential subfamily member 1 (TRPA1) agonist (allyl isothiocyanate, AITC) increased the production of ROS and the level of [Ca(2+)]c in A549 cell. Moreover, HC-030031, a TRPA1 selective antagonist, significantly inhibited the enhanced ROS and [Ca(2+)]c induced by AITC or cold stimulation, respectively. Taken together, these data demonstrated that TRPA1 activation played an important role in the enhanced production of ROS induced by cold stress in A549 cell.

  20. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation

    PubMed Central

    Kato, Yoji

    2016-01-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  1. Reactive oxygen species formation and bystander effects in gradient irradiation on human breast cancer cells

    PubMed Central

    Rong, Yi; Lee, Shin Hee; Wu, Shiyong; Zuo, Li

    2016-01-01

    Ionizing radiation (IR) in cancer radiotherapy can induce damage to neighboring cells via non-targeted effects by irradiated cells. These so-called bystander effects remain an area of interest as it may provide enhanced efficacy in killing carcinomas with minimal radiation. It is well known that reactive oxygen species (ROS) are ubiquitous among most biological activities. However, the role of ROS in bystander effects has not been thoroughly elucidated. We hypothesized that gradient irradiation (GI) has enhanced therapeutic effects via the ROS-mediated bystander pathways as compared to uniform irradiation (UI). We evaluated ROS generation, viability, and apoptosis in breast cancer cells (MCF-7) exposed to UI (5 Gy) or GI (8–2 Gy) in radiation fields at 2, 24 and 48 h after IR. We found that extracellular ROS release induced by GI was higher than that by UI at both 24 h (p < 0.001) and 48 h (p < 0.001). More apoptosis and less viability were observed in GI when compared to UI at either 24 h or 48 h after irradiation. The mean effective doses (ED) of GI were ~130% (24 h) and ~48% (48 h) higher than that of UI, respectively. Our results suggest that GI is superior to UI regarding redox mechanisms, ED, and toxic dosage to surrounding tissues. PMID:27223435

  2. Superparamagnetic iron oxide nanoparticles as radiosensitizer via enhanced reactive oxygen species formation

    SciTech Connect

    Klein, Stefanie; Sommer, Anja; Distel, Luitpold V.R.; Neuhuber, Winfried; Kryschi, Carola

    2012-08-24

    Highlights: Black-Right-Pointing-Pointer Ultrasmall citrate-coated SPIONs with {gamma}Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} structure were prepared. Black-Right-Pointing-Pointer SPIONs uptaken by MCF-7 cells increase the ROS production for about 240%. Black-Right-Pointing-Pointer The SPION induced ROS production is due to released iron ions and catalytically active surfaces. Black-Right-Pointing-Pointer Released iron ions and SPION surfaces initiate the Fenton and Haber-Weiss reaction. Black-Right-Pointing-Pointer X-ray irradiation of internalized SPIONs leads to an increase of catalytically active surfaces. -- Abstract: Internalization of citrate-coated and uncoated superparamagnetic iron oxide nanoparticles by human breast cancer (MCF-7) cells was verified by transmission electron microscopy imaging. Cytotoxicity studies employing metabolic and trypan blue assays manifested their excellent biocompatibility. The production of reactive oxygen species in iron oxide nanoparticle loaded MCF-7 cells was explained to originate from both, the release of iron ions and their catalytically active surfaces. Both initiate the Fenton and Haber-Weiss reaction. Additional oxidative stress caused by X-ray irradiation of MCF-7 cells was attributed to the increase of catalytically active iron oxide nanoparticle surfaces.

  3. Formation of copper oxychloride and reactive oxygen species as causes of uterine injury during copper oxidation of Cu-IUD.

    PubMed

    Beltran-Garcia, M J; Espinosa, A; Herrera, N; Perez-Zapata, A J; Beltran-Garcia, C; Ogura, T

    2000-02-01

    The lining of the uterus and cervix might be injured by a variety of oxidation products of Cu in a Cu-IUD, including cuprous ions, dissolved and precipitated cupric ions, and reactive oxygen species such as superoxide radicals, hydrogen peroxide, and hydroxyl radicals. In this study, the human amnious WISH cell line was employed as a model of uterine cells in the presence of copper. The cell viability was decreased by elemental copper, which was alleviated up to 70% by the addition of catalase. The addition of copper oxychloride caused cell death in a dose-dependent manner. Hydroxyl radicals in the presence of copper were determined by the formation of malondialdehyde. Soluble cuprous chloride complexes are formed in the uterus by slowly entering oxygen. The complexes are partly oxidized to insoluble copper oxychloride. which damages the endometrium. Unoxidized cuprous ions migrate to the oxygen-rich cervix and are oxidized to copper oxychloride, causing cervix damage.

  4. Reactive oxygen species formation and apoptosis in human peripheral blood mononuclear cell induced by 900 MHz mobile phone radiation.

    PubMed

    Lu, Yao-Sheng; Huang, Bao-Tian; Huang, Yao-Xiong

    2012-01-01

    We demonstrate that reactive oxygen species (ROS) plays an important role in the process of apoptosis in human peripheral blood mononuclear cell (PBMC) which is induced by the radiation of 900 MHz radiofrequency electromagnetic field (RFEMF) at a specific absorption rate (SAR) of ~0.4 W/kg when the exposure lasts longer than two hours. The apoptosis is induced through the mitochondrial pathway and mediated by activating ROS and caspase-3, and decreasing the mitochondrial potential. The activation of ROS is triggered by the conformation disturbance of lipids, protein, and DNA induced by the exposure of GSM RFEMF. Although human PBMC was found to have a self-protection mechanism of releasing carotenoid in response to oxidative stress to lessen the further increase of ROS, the imbalance between the antioxidant defenses and ROS formation still results in an increase of cell death with the exposure time and can cause about 37% human PBMC death in eight hours.

  5. Analysis of liquid water formation in polymer electrolyte membrane (PEM) fuel cell flow fields with a dry cathode supply

    NASA Astrophysics Data System (ADS)

    Gößling, Sönke; Klages, Merle; Haußmann, Jan; Beckhaus, Peter; Messerschmidt, Matthias; Arlt, Tobias; Kardjilov, Nikolay; Manke, Ingo; Scholta, Joachim; Heinzel, Angelika

    2016-02-01

    PEM fuel cells can be operated within a wide range of different operating conditions. In this paper, the special case of operating a PEM fuel cell with a dry cathode supply and without external humidification of the cathode, is considered. A deeper understanding of the water management in the cells is essential for choosing the optimal operation strategy for a specific system. In this study a theoretical model is presented which aims to predict the location in the flow field at which liquid water forms at the cathode. It is validated with neutron images of a PEM fuel cell visualizing the locations at which liquid water forms in the fuel cell flow field channels. It is shown that the inclusion of the GDL diffusion resistance in the model is essential to describe the liquid water formation process inside the fuel cell. Good agreement of model predictions and measurement results has been achieved. While the model has been developed and validated especially for the operation with a dry cathode supply, the model is also applicable to fuel cells with a humidified cathode stream.

  6. Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liggio, J.; Staebler, R.; Li, S.-M.

    2015-06-01

    As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) is studied in a smog chamber equipped with a High Resolution Time-of-Flight Aerosol Mass Spectrometer and a Quantum Cascade Laser instrument. A large diversity of nitrogen containing organic (NOC) fragments was observed which were consistent with the reaction of ammonia with carbonyl containing SOA. The uptake coefficients of NH3 to SOA leading to organonitrogen compounds are reported for the first time and were in the range of ∼ 10-3-10-2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (∼ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt% to the total α-pinene and m-xylene derived SOA, and 4-15 wt% of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen, and a mechanism for medium or long-range transport and dry/wet deposition of atmospheric nitrogen.

  7. Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liggio, J.; Staebler, R.; Li, S.-M.

    2015-12-01

    As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) was studied in a smog chamber equipped with a high resolution time-of-flight aerosol mass spectrometer and a quantum cascade laser instrument. A large diversity of nitrogen-containing organic (NOC) fragments was observed which were consistent with the reactions between ammonia and carbonyl-containing SOA. Ammonia uptake coefficients onto SOA which led to organonitrogen compounds were reported for the first time, and were in the range of ∼ 10-3-10-2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (~ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt % to the total α-pinene- and m-xylene-derived SOA, respectively, and 4-15 wt % of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen. This mechanism may also contribute to the medium or long-range transport and wet/dry deposition of atmospheric nitrogen.

  8. Relationships Between Molecular Structure and Chemical Reactivity in Hypergolic Ionic Liquids: Progress Toward Designing Green Fuels for Bipropellant Applications

    DTIC Science & Technology

    2012-05-01

    reaction within 10 ms from the time when mixed with oxidizers such as white fuming nitric acid (WFNA, ~100% HNO3), inhibited red fuming nitric acid ...dropped into excess white-fuming nitric acid (1.0-1.5 mL). The ignition delay times were recorded in triplicate at 500 frames/s using an Olympus i...smart fuels that can be custom tailored to react with an oxidizer of choice for specific bipropellant applications. 3 Non- corrosive fuels that

  9. NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

    SciTech Connect

    Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2016-04-18

    The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  10. [Impact of biologically important anions on reactive oxygen species formation in water under the effect of non-ionizing physical agents].

    PubMed

    Gudkov, S V; Ivanov, V E; Karp, O É; Chernikov, A V; Belosludtsev, K N; Bobylev, A G; Astashev, M E; Gapeev, A B; Bruskov, V I

    2014-01-01

    The influence of biologically relevant anions (succinate, acetate, citrate, chloride, bicarbonate, hydroorthophosphate, dihydroorthophosphate, nitrite, nitrate) on the formation of hydrogen peroxide and hydroxyl radicals in water was studied under the effect of non-ionizing radiation: heat, laser light with a wavelength of 632.8 nm, corresponding to the maximum absorption of molecular oxygen, and electromagnetic radiation of extremely high frequencies. It has been established that various anions may both inhibit the formation of reactive oxygen species and increase it. Bicarbonate and sulfate anions included in the biological fluids' and medicinal mineral waters have significant, but opposite effects on reactive oxygen species production. Different molecular mechanisms of reactive oxygen species formation are considered under the action of the investigated physical factors involving these anions, which may influence the biological processes by signal-regulatory manner and provide a healing effect in physical therapy.

  11. Aminoguanidine inhibits reactive oxygen species formation, lipid peroxidation, and oxidant-induced apoptosis.

    PubMed

    Giardino, I; Fard, A K; Hatchell, D L; Brownlee, M

    1998-07-01

    Aminoguanidine (AG) treatment, like nerve growth factor (NGF) treatment, prevents diabetes-induced apoptosis of retinal Müller cells in the rat eye, but the mechanism involved is unknown. In this study, the effects of preincubation with AG on oxidant-induced apoptosis, oxidant-induced intracellular reactive oxygen species (ROS) production, and lipid peroxidation were determined in rat retinal Müller cells and compared with the effects of NGF, a protein that protects neuronal cells from oxidative stress. The effect of AG on rabbit vitreous lipid peroxide levels was also determined. After exposure to increasing concentrations of H2O2, there was a corresponding increase in the percentage of apoptotic Müller cells. Preincubation with AG for 48 h completely inhibited oxidant-induced apoptosis in response to 10 micromol/l H2O2 (+AG 0 vs. 10 micromol/l, NS), and reduced the percentage of apoptotic cells in response to 50 micromol/l H2O2 by 50% (+AG vs. -AG, P < 0.01). Longer preincubation did not increase the antiapoptotic effect of AG. The effect of AG was dose-dependent. Similar results were obtained after preincubation with NGF. Both AG and NGF preincubation prevented the twofold increase in oxidant-induced lipid peroxides. The fivefold increase in oxidant-induced ROS production was decreased 100% by NGF, but only 61% by AG preincubation. The twofold increase in vitreous lipid peroxide level in diabetic rabbits was completely prevented by AG treatment. AG reduced H2O2-induced benzoate hydroxylation in a dose-dependent manner. Intracellular glutathione content was unchanged. These data demonstrate that AG can act as an antioxidant in vivo, quenching hydroxyl radicals and lipid peroxidation in cells and tissues and preventing oxidant-induced apoptosis.

  12. Role of sulfonation in the stability, reactivity, and selectivity of poly(ether imide) used to develop ion exchange membranes: DFT study with application to fuel cells.

    PubMed

    López-Chávez, Ernesto; Peña-Castañeda, Yésica A; de la Portilla-Maldonado, L César; Guzmán-Pantoja, Javier; Martínez-Magadán, José Manuel; Oviedo-Roa, Raúl; de Landa Castillo-Alvarado, Fray; Cruz-Torres, Armando

    2014-07-01

    The design of polymer electrolyte membranes for fuel cells must satisfy two equally important fundamental principles: optimization of the reactivity and the selectivity in order to improve the ion transport properties of the membrane as well as its long-term stability in the hydrated state at high temperature (above 100 °C). A study utilizing density functional theory (DFT) to elucidate the effect of the degree of sulfonation on the chemical stability, reactivity, and selectivity of poly(ether imide) (PEI), which allows the ionic transport properties of the membrane to be predicted, is reported here. Sulfonated poly(ether imide) (SPEI) structures with (-SO3H) n (n = 1-6) groups were built and optimized in order to calculate the above properties as functions of the number of sulfonyl groups. A comparative study demonstrated that the SPEI with four sulfonyl groups in its backbone is the polymer with the properties best suited for use in fuel cells.

  13. Ash particulate formation from pulverized coal under oxy-fuel combustion conditions.

    PubMed

    Jia, Yunlu; Lighty, JoAnn S

    2012-05-01

    Aerosol particulates are generated by coal combustion. The amount and properties of aerosol particulates, specifically size distribution and composition, can be affected by combustion conditions. Understanding the formation of these particles is important for predicting emissions and understanding potential deposition. Oxy-fuel combustion conditions utilize an oxygen-enriched gas environment with CO(2). The high concentration of CO(2) is a result of recycle flue gas which is used to maintain temperature. A hypothesis is that high CO(2) concentration reduces the vaporization of refractory oxides from combustion. A high-temperature drop-tube furnace was used under different oxygen concentrations and CO(2) versus N(2) to study the effects of furnace temperature, coal type, and gas phase conditions on particulate formation. A scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) were utilized for particle size distributions ranging from 14.3 nm to 20 μm. In addition, particles were collected on a Berner low pressure impactor (BLPI) for elemental analysis using scanning electron microscopy and energy dispersive spectroscopy. Three particle size modes were seen: ultrafine (below 0.1 μm), fine (0.1 to 1.0 μm), and coarse (above 1 μm). Ultrafine mass concentrations were directly related to estimated particle temperature, increasing with increasing temperature. For high silicon and calcium coals, Utah Skyline and PRB, there was a secondary effect due to CO(2) and the hypothesized reaction. Illinois #6, a high sulfur coal, had the highest amount of ultrafine mass and most of the sulfur was concentrated in the ultrafine and fine modes. Fine and coarse mode mass concentrations did not show a temperature or CO(2) relationship. (The table of contents graphic and abstract graphic are adapted from ref 27.).

  14. In situ formation of graphene layers on graphite surfaces for efficient anodes of microbial fuel cells.

    PubMed

    Tang, Jiahuan; Chen, Shanshan; Yuan, Yong; Cai, Xixi; Zhou, Shungui

    2015-09-15

    Graphene can be used to improve the performance of the anode in a microbial fuel cell (MFC) due to its good biocompatibility, high electrical conductivity and large surface area. However, the chemical production and modification of the graphene on the anode are environmentally hazardous because of the use of various harmful chemicals. This study reports a novel method based on the electrochemical exfoliation of a graphite plate (GP) for the in situ formation of graphene layers on the surface of a graphite electrode. When the resultant graphene-layer-based graphite plate electrode (GL/GP) was used as an anode in an MFC, a maximum power density of 0.67 ± 0.034 W/m(2) was achieved. This value corresponds to 1.72-, 1.56- and 1.26-times the maximum power densities of the original GP, exfoliated-graphene-modified GP (EG/GP) and chemically-reduced-graphene-modified GP (rGO/GP) anodes, respectively. Electrochemical measurements revealed that the high performance of the GL/GP anode was attributable to its macroporous structure, improved electron transfer and high electrochemical capacitance. The results demonstrated that the proposed method is a facile and environmentally friendly synthesis technique for the fabrication of high-performance graphene-based electrodes for use in microbial energy harvesting.

  15. Silica colloid formation enhances performance of sediment microbial fuel cells in a low conductivity soil.

    PubMed

    Domínguez-Garay, Ainara; Berná, Antonio; Ortiz-Bernad, Irene; Esteve-Núñez, Abraham

    2013-02-19

    The performance of sediment microbial fuel cells (SMFCs) is usually limited by the structure, moisture, and salt content of the soil where they are allocated. Despite the influence of soil, so far most of efforts to improve SMFCs have been limited to the hardware design of the bioelectrochemical device. Our main objective was to enhance performance of SMFCs by stimulating the in situ formation of silica colloids in a low conductivity rice paddy soil. Our results have revealed that the presence of a silica colloid network, described by cryo-SEM analysis, reduced soil resistivity, enhanced ion mobility and consequently enhanced the power production by a factor of 10. Furthermore, our silica-supplemented soil showed better utilization of the electron donor, either acetate or natural rice root exudates, by electrogenic microbial populations. Sustainable manipulation of soil micromorphology using environmentally friendly reagents such as silica offers a novel approach for enhancing the performance of in situ microbial electrochemical applications in low conductivity soils, thus silica colloid geoengineering should be considered as part of future applications of SMFCs.

  16. Formation mechanism of gas bubble superlattice in UMo metal fuels: Phase-field modeling investigation

    SciTech Connect

    Hu, Shenyang; Burkes, Douglas E.; Lavender, Curt A.; Senor, David J.; Setyawan, Wahyu; Xu, Zhijie

    2016-07-08

    Nano-gas bubble superlattices are often observed in irradiated UMo nuclear fuels. However, the for- mation mechanism of gas bubble superlattices is not well understood. A number of physical processes may affect the gas bubble nucleation and growth; hence, the morphology of gas bubble microstructures including size and spatial distributions. In this work, a phase-field model integrating a first-passage Monte Carlo method to investigate the formation mechanism of gas bubble superlattices was devel- oped. Six physical processes are taken into account in the model: 1) heterogeneous generation of gas atoms, vacancies, and interstitials informed from atomistic simulations; 2) one-dimensional (1-D) migration of interstitials; 3) irradiation-induced dissolution of gas atoms; 4) recombination between vacancies and interstitials; 5) elastic interaction; and 6) heterogeneous nucleation of gas bubbles. We found that the elastic interaction doesn’t cause the gas bubble alignment, and fast 1-D migration of interstitials along $\\langle$110$\\rangle$ directions in the body-centered cubic U matrix causes the gas bubble alignment along $\\langle$110$\\rangle$ directions. It implies that 1-D interstitial migration along [110] direction should be the primary mechanism of a fcc gas bubble superlattice which is observed in bcc UMo alloys. Simulations also show that fission rates, saturated gas concentration, and elastic interaction all affect the morphology of gas bubble microstructures.

  17. Structural insights into dynamics of RecU–HJ complex formation elucidates key role of NTR and stalk region toward formation of reactive state

    PubMed Central

    Khavnekar, Sagar; Dantu, Sarath Chandra; Sedelnikova, Svetlana; Ayora, Sylvia; Rafferty, John; Kale, Avinash

    2017-01-01

    Holliday junction (HJ) resolving enzyme RecU is involved in DNA repair and recombination. We have determined the crystal structure of inactive mutant (D88N) of RecU from Bacillus subtilis in complex with a 12 base palindromic DNA fragment at a resolution of 3.2 Å. This structure shows the stalk region and the essential N-terminal region (NTR) previously unseen in our DNA unbound structure. The flexible nature of the NTR in solution was confirmed using SAXS. Thermofluor studies performed to assess the stability of RecU in complex with the arms of an HJ indicate that it confers stability. Further, we performed molecular dynamics (MD) simulations of wild type and an NTR deletion variant of RecU, with and without HJ. The NTR is observed to be highly flexible in simulations of the unbound RecU, in agreement with SAXS observations. These simulations revealed domain dynamics of RecU and their role in the formation of complex with HJ. The MD simulations also elucidate key roles of the NTR, stalk region, and breathing motion of RecU in the formation of the reactive state. PMID:27903910

  18. Structural insights into dynamics of RecU-HJ complex formation elucidates key role of NTR and stalk region toward formation of reactive state.

    PubMed

    Khavnekar, Sagar; Dantu, Sarath Chandra; Sedelnikova, Svetlana; Ayora, Sylvia; Rafferty, John; Kale, Avinash

    2017-01-25

    Holliday junction (HJ) resolving enzyme RecU is involved in DNA repair and recombination. We have determined the crystal structure of inactive mutant (D88N) of RecU from Bacillus subtilis in complex with a 12 base palindromic DNA fragment at a resolution of 3.2 Å. This structure shows the stalk region and the essential N-terminal region (NTR) previously unseen in our DNA unbound structure. The flexible nature of the NTR in solution was confirmed using SAXS. Thermofluor studies performed to assess the stability of RecU in complex with the arms of an HJ indicate that it confers stability. Further, we performed molecular dynamics (MD) simulations of wild type and an NTR deletion variant of RecU, with and without HJ. The NTR is observed to be highly flexible in simulations of the unbound RecU, in agreement with SAXS observations. These simulations revealed domain dynamics of RecU and their role in the formation of complex with HJ. The MD simulations also elucidate key roles of the NTR, stalk region, and breathing motion of RecU in the formation of the reactive state.

  19. Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Clary, D. W.; Ramachandra, M. K.

    1985-01-01

    Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation.

  20. Calcite formation in soft coral sclerites is determined by a single reactive extracellular protein.

    PubMed

    Rahman, M Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-09-09

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature.

  1. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    PubMed Central

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  2. Synthetic fuel combustion: pollutant formation. Soot initiation mechanisms in burning aromatics. First quarterly report, 19 September-31 December 1980

    SciTech Connect

    Rawlins, W. T.; Tanzawa, T.

    1981-01-01

    Although considerable progress has been made in recent years in understanding the phenomenology of soot formation in the combustion of hydrocarbon fuels, relatively little attention has been focused upon aromatic fuels of the types commonly found in coal liquids. In particular, the effects of gas-phase free radicals, formed during combustion, on the kinetics of formation of incipient soot particles have not been characterized. Accordingly, an experimental investigation of the detailed kinetics of incipient soot formation in the combustion and pyrolysis of aromatic fuels of the benzene, anisole, phenol, and pyrrole families has been initiated in order to determine soot formation mechanisms and rate parameters. The experiments will be performed in a shock tube over the temperature range 1300 to 2500 K, using multiple ultraviolet, visible, and infrared diagnostics to monitor the kinetic behavior of free radicals (such as OH), incipient soot particles, and combustion products. Experiments will be conducted with artificially enhanced concentrations of free radicals such as OH and O to determine their effects on the kinetics of soot and soot precursors. The experimental work will be supported and directed by a parallel analytical effort using a detailed mechanistic model of the chemical kinetics and dynamics of the reacting systems. In this report, the design and configuration of the experimental apparatus are described, the details of the kinetic model are outlined, and possible reaction pathways are discussed.

  3. The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame.

    PubMed

    Hansen, N; Li, W; Law, M E; Kasper, T; Westmoreland, P R; Yang, B; Cool, T A; Lucassen, A

    2010-10-14

    Fuel decomposition and benzene formation processes in a premixed, laminar, low-pressure, fuel-rich flame of 1-hexene (C(6)H(12), CH(2)=CH-CH(2)-CH(2)-CH(2)-CH(3)) are investigated by comparing quantitative mole fraction profiles of flame species with kinetic modeling results. The premixed flame, which is stabilized on a flat-flame burner under a reduced pressure of 30 Torr (= 40 mbar), is analyzed by flame-sampling molecular-beam time-of-flight mass spectrometry which uses photoionization by tunable vacuum-ultraviolet synchrotron radiation. The temperature profile of the flame is measured by OH laser-induced fluorescence. The model calculations include the latest rate coefficients for 1-hexene decomposition (J. H. Kiefer et al., J. Phys. Chem. A, 2009, 113, 13570) and for the propargyl (C(3)H(3)) + allyl (a-C(3)H(5)) reaction (J. A. Miller et al., J. Phys. Chem. A, 2010, 114, 4881). The predicted mole fractions as a function of distance from the burner are acceptable and often even in very good agreement with the experimentally observed profiles, thus allowing an assessment of the importance of various fuel decomposition reactions and benzene formation routes. The results clearly indicate that in contrast to the normal reactions of fuel destruction by radical attack, 1-hexene is destroyed mainly by decomposition via unimolecular dissociation forming allyl (a-C(3)H(5)) and n-propyl (n-C(3)H(7)). Minor fuel-consumption pathways include H-abstraction reactions producing various isomeric C(6)H(11) radicals with subsequent β-scissions into C(2), C(3), and C(4) intermediates. The reaction path analysis also highlights a significant contribution through the propargyl (C(3)H(3)) + allyl (a-C(3)H(5)) reaction to the formation of benzene. In this flame, benzene is dominantly formed through H-assisted isomerization of fulvene, which itself is almost exclusively produced by the C(3)H(3) + a-C(3)H(5) reaction.

  4. Long term deposit formation in aviation turbine fuel at elevated temperature

    NASA Technical Reports Server (NTRS)

    Giovanetti, A. J.; Szetela, E. J.

    1986-01-01

    An experimental characterization is conducted for the relationships between deposit mass, operating time, and temperature, in coking associated with aviation fuels under conditions simulating those typical of turbine engine fuel systems. Jet A and Suntech A fuels were tested in stainless steel tubing heated to 420-750 K, over test durations of between 3 and 730 hr and at fuel velocities of 0.07-1.3 m/sec. Deposit rates are noted to be a strong function of tube temperature; for a given set of test conditions, deposition rates for Suntech A exceed those of Jet A by a factor of 10. Deposition rates increased markedly with test duration for both fuels. The heated tube data obtained are used to develop a global chemical kinetic model for fuel oxidation and carbon deposition.

  5. Phlorotannins from brown algae (Fucus vesiculosus) inhibited the formation of advanced glycation endproducts by scavenging reactive carbonyls.

    PubMed

    Liu, Haiyan; Gu, Liwei

    2012-02-08

    Accumulation of advanced glycation end products (AGEs) in vivo is associated with aging, diabetes, Alzheimer's disease, renal failure, etc. The objective of this study was to investigate the inhibitory effects of brown algae Fucus vesiculosus phlorotannins on the formation of AGEs. F. vesiculosus phlorotannins were extracted using 70% acetone. The resultant extract was fractionated into dichloromethane, ethyl acetate, butanol, and water fractions. The ethyl acetate fraction was further fractionated into four subfractions (Ethyl-F1 to -F4) using a Sephadex LH-20 column. F. vesiculosus acetone extract or fractions significantly inhibited the formation of AGEs mediated by glucose and methylglyoxal in a concentration-dependent manner. The concentrations of F. vesiculosus extracts required to inhibit 50% of albumin glycation (EC(50)) in the bovine serum albumin (BSA)-methylglyoxal assay were lower than those of aminoguanidine (a drug candidate for diabetic complication), except for F. vesiculosus acetone extract and dichloromethane fraction. In the BSA-glucose assay, F. vesiculosus extracts inhibited BSA glycation more than or as effectively as aminoguanidine, except for Ethyl-F3 and -F4. The ethyl acetate fraction and its four subfractions scavenged more than 50% of methylglyoxal in two hours. The hypothesis whether F. vesiculosus phlorotannins scavenged reactive carbonyls by forming adducts was tested. Phloroglucinol, the constituent unit of phlorotannins, reacted with glyoxal and methylglyoxal. Five phloroglucinol-carbonyl adducts were detected and tentatively identified using HPLC-ESI-MS(n).

  6. The reduction of reactive oxygen species formation by mitochondrial alternative respiration in tomato basal defense against TMV infection.

    PubMed

    Liao, Yang-Wen-Ke; Shi, Kai; Fu, Li-Jun; Zhang, Shuai; Li, Xin; Dong, De-Kun; Jiang, Yu-Ping; Zhou, Yan-Hong; Xia, Xiao-Jian; Liang, Wu-Sheng; Yu, Jing-Quan

    2012-02-01

    The role of mitochondrial alternative oxidase (AOX) and the relationship between systemic AOX induction, ROS formation, and systemic plant basal defense to Tobacco mosaic virus (TMV) were investigated in tomato plants. The results showed that TMV inoculation significantly increased the level of AOX gene transcripts, ubiquinone reduction levels, pyruvate content, and cyanide-resistant respiration (CN-resistant R) in upper, un-inoculated leaves. Pretreatment with potassium cyanide (KCN, a cytochrome pathway inhibitor) greatly increased CN-resistant R and reduced reactive oxygen species (ROS) formation, while application of salicylhydroxamic acid (SHAM, an AOX inhibitor) blocked the AOX activity and enhanced the production of ROS in the plants. Furthermore, TMV systemic infection was enhanced by SHAM and reduced by KCN pretreatment, as compared with the un-pretreated TMV counterpart. In addition, KCN application significantly diminished TMV-induced increase in antioxidant enzyme activities and dehydroascorbate/total ascorbate pool, while an opposite change was observed with SHAM-pretreated plants. These results suggest that the systemic induction of the mitochondrial AOX pathway plays a critical role in the reduction of ROS to enhance basal defenses. Additional antioxidant systems were also coordinately regulated in the maintenance of the cellular redox homeostasis.

  7. Influence of oestrogens on formation of reactive oxygen species in liver microsomes of differently aged male Wistar rats.

    PubMed

    Barth, A; Landmann, G; Liepold, K; Zapf, H; Müller, D; Karge, E; Klinger, W

    1999-07-01

    Metabolic pathways of oestrogens are the formation of catechol oestrogens (CE; 2- and 4-hydroxy-oestrogens), redox cycling of CE and free radical generation, mediated through cytochrome P450 (P450) oxidase/reductase activity. We checked the oestrogens oestradiol (E2), oestradiol valerate (E2V) and ethinyloestradiol (EE2) for formation of reactive oxygen species in vitro and ex vivo in male Wistar rats in dependence on age. In liver microsomes of 10-, 30-, 60- and 270-day-old rats the influence of E2, E2V and EE2 (10(-7)-10(-3) M) on NADPH-Fe(++)-stimulated lipid peroxidation (LPO), H2O2 generation and lucigenin (LUC) and luminol (LUM) amplified chemiluminescence (CL) was investigated. The same parameters, additionally P450 content and monooxygenase activities were measured in liver 9000 x g supernatants after subchronic administration of the oestrogens (1, 10 mg/kg b. wt. orally). The most important results are the strong inhibitory capacities of the oestrogens in vitro on LPO in the order of E2V < E2 < EE2, most pronounced in 10-, 60- and 270-day-old animals. In microsomes of 30-day-old rats with the highest control LPO the antioxidative effect of the oestrogens was lower. Whereas the H2O2 generation was not changed by E2, enhanced by E2V, but diminished by EE2 in all age groups, CL(LUC) and CL(LUM) were inhibited in the order of E2 < E2V < EE2. Also after subchronical treatment of the rats the antioxidative action of the oestrogens was evident, microsomal LPO was inhibited in the order of E2 < E2V < EE2. All oestrogens inhibited ethylmorphine N-demethylation. But enhanced H2O2 generation and increased CL(LUC) also indicate a formation of reactive oxygen species by these oestrogens. Obviously in vitro the antioxidative phenolic structure of the oestrogens dominates, whereas after in vivo administration the dose- and age-dependent biotransformation produces prooxidative in addition to antioxidative structures.

  8. Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions

    SciTech Connect

    Alfassi, Z.B.; Khaikin, G.I.; Neta, P. )

    1995-01-05

    Aryl radicals (phenyl, 4-biphenylyl, 2-naphthyl, 1-naphthyl, and 9-phenanthryl) were produced by the reaction of the corresponding aryl bromide with solvated electrons and reacted rapidly with oxygen to produce the arylperoxyl radicals. These radicals exhibit optical absorptions in the visible range, with [lambda][sub max] at 470, 550, 575, 650, and 700 nm, respectively. Arylperoxyl radicals react with 2,2[prime]-azinobis(3-ethylbenzothiazoiine-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation products as a function of substrate concentration, vary between 4 [times] 10[sup 6] and 2 [times] 10[sup 9] L mol[sup [minus]1] s[sup [minus]1] and increase in the order phenyl-, 4-biphenyl-, 2-naphthyl-, 1-naphthyl-, and 9-phenanthrylperoxyl, the same order as the absorption peaks of these radicals. Good correlation was found between log k and the energy of the absorption peak. 16 refs., 2 figs., 2 tabs.

  9. Combustion characteristics and air pollutant formation during oxy-fuel co-combustion of microalgae and lignite.

    PubMed

    Gao, Yuan; Tahmasebi, Arash; Dou, Jinxiao; Yu, Jianglong

    2016-05-01

    Oxy-fuel combustion of solid fuels is seen as one of the key technologies for carbon capture to reduce greenhouse gas emissions. The combustion characteristics of lignite coal, Chlorella vulgaris microalgae, and their blends under O2/N2 and O2/CO2 conditions were studied using a Thermogravimetric Analyzer-Mass Spectroscopy (TG-MS). During co-combustion of blends, three distinct peaks were observed and were attributed to C. vulgaris volatiles combustion, combustion of lignite, and combustion of microalgae char. Activation energy during combustion was calculated using iso-conventional method. Increasing the microalgae content in the blend resulted in an increase in activation energy for the blends combustion. The emissions of S- and N-species during blend fuel combustion were also investigated. The addition of microalgae to lignite during air combustion resulted in lower CO2, CO, and NO2 yields but enhanced NO, COS, and SO2 formation. During oxy-fuel co-combustion, the addition of microalgae to lignite enhanced the formation of gaseous species.

  10. Delineating the relationships among the formation of reactive oxygen species, cell membrane instability and innate autoimmunity in intestinal reperfusion injury.

    PubMed

    Lee, Haekyung; Ko, Eun Hee; Lai, Mark; Wei, Na; Balroop, Javi; Kashem, Zerin; Zhang, Ming

    2014-04-01

    Acute intestinal ischemia is a medical emergency with a high mortality rate, attesting to the need for a better understanding of its pathogenesis and the development of effective therapies. The goal of this study was to delineate the relationships among intracellular and extracellular events in intestinal ischemia/reperfusion (I/R) injury, particularly the formation of reactive oxygen species (ROS), cell membrane instability associated with lipid peroxidation and the innate autoimmune response mediated by natural IgM and complement. A murine model of natural IgM-mediated intestinal I/R was used. Mice overexpressing anti-oxidant enzyme SOD1 were found to have significantly reduced intestinal tissue damage and complete blockage of IgM-mediated complement activation compared with WT controls. To determine if cell membrane instability was an event intermediate between ROS formation and natural IgM-mediated innate autoimmune response, the cell membrane stabilizer (trehalose) was administered to WT mice prior to the induction of intestinal ischemia. Treatment with trehalose significantly protected animals from I/R injury and inhibited IgM-mediated complement activation although it did not prevent membrane lipid peroxidation. These data indicate that in normal mice subjected to I/R injury, intracellular ROS formation is an event upstream of the lipid peroxidation which results in cell membrane instability. The membrane instability leads to an innate autoimmune response by natural IgM and complement. Trehalose, a nontoxic disaccharide tolerated well by animals and humans, has promise as a protective agent for patients with medical conditions related to acute intestinal ischemia.

  11. Hydroxyl radical formation during ozonation of multiwalled carbon nanotubes: performance optimization and demonstration of a reactive CNT filter.

    PubMed

    Oulton, Rebekah; Haase, Jason P; Kaalberg, Sara; Redmond, Connor T; Nalbandian, Michael J; Cwiertny, David M

    2015-03-17

    We explored factors influencing hydroxyl radical (•OH) formation during ozonation of multiwalled carbon nanotubes (MWCNTs) and assessed this system's viability as a next-generation advanced oxidation process (AOP). Using standard reactivity metrics for ozone-based AOPs (RCT values), MWCNTs promoted •OH formation during ozonation to levels exceeding ozone (both alone and with activated carbon) and equivalent to ozone with hydrogen peroxide. MWCNTs oxidized with nitric acid exhibited vastly greater rates of ozone consumption and •OH formation relative to as-received MWCNTs. While some of this enhancement reflects their greater suspension stability, a strong correlation between RCT values and surface oxygen concentrations from X-ray photoelectron spectroscopy suggests that surface sites generated during MWCNT oxidation promote •OH exposure. Removal of several ozone-recalcitrant species [para-chlorobenzoic acid (p-CBA), atrazine, DEET, and ibuprofen] was not significantly inhibited in the presence of radical scavengers (humic acid, carbonate), in complex aquatic matrices (Iowa River water) and after 12 h of continuous exposure of MWCNTs to concentrated ozone solutions. As a proof-of-concept, oxidized MWCNTs deposited on a ceramic membrane chemically oxidized p-CBA in a flow through system, with removal increasing with influent ozone concentration and mass of deposited MWCNTs (in mg/cm2). This hybrid membrane platform, which integrates adsorption, oxidation, and filtration via an immobilized MWCNT layer, may serve as the basis for future novel nanomaterial-enabled technologies, although long-term performance trials under representative treatment scenarios remain necessary.

  12. Ambient Fine Particulate Matter Suppresses In Vivo Proliferation of Bone Marrow Stem Cells through Reactive Oxygen Species Formation

    PubMed Central

    Cui, Yuqi; Jia, Fengpeng; He, Jianfeng; Xie, Xiaoyun; Li, Zhihong; Fu, Minghuan; Hao, Hong; Liu, Ying; Liu, Dylan Z.; Cowan, Peter J.; Zhu, Hua; Sun, Qinghua; Liu, Zhenguo

    2015-01-01

    Aims Some environmental insults, such as fine particulate matter (PM) exposure, significantly impair the function of stem cells. However, it is unknown if PM exposure could affect the population of bone marrow stem cells (BMSCs). The present study was to investigate the effects of PM on BMSCs population and related mechanism(s). Main Metheods PM was intranasally distilled into male C57BL/6 mice for one month. Flow cytometry with antibodies for BMSCs, Annexin V and BrdU ware used to determine the number of BMSCs and the levels of their apoptosis and proliferation in vivo. Phosphorylated Akt (P-Akt) level was determined in the BM cells with western blotting. Intracellular reactive oxygen species (ROS) formation was quantified using flow cytometry analysis. To determine the role of PM-induced ROS in BMSCs population, proliferation, and apotosis, experiments were repeated using N-acetylcysteine (NAC)-treated wild type mice or a triple transgenic mouse line with overexpression of antioxidant network (AON) composed of superoxide dismutase (SOD)1, SOD3, and glutathione peroxidase-1 with decreased in vivo ROS production. Key Findings PM treatment significantly reduced BMSCs population in association with increased ROS formation, decreased P-Akt level, and inhibition of proliferation of BMSCs without induction of apoptosis. NAC treatment or AON overexpression with reduced ROS formation effectively prevented PM-induced reduction of BMSCs population and proliferation with partial recovery of P-Akt level. Significance PM exposure significantly decreased the population of BMSCs due to diminished proliferation via ROS-mediated mechanism (could be partially via inhibition of Akt signaling). PMID:26058063

  13. In situ time-resolved X-ray diffraction of tobermorite formation in autoclaved aerated concrete: Influence of silica source reactivity and Al addition

    SciTech Connect

    Matsui, Kunio; Kikuma, Jun; Tsunashima, Masamichi; Ishikawa, Tetsuji; Matsuno, Shin-ya; Ogawa, Akihiro; Sato, Masugu

    2011-05-15

    The hydrothermal formation of tobermorite during the processing of autoclaved aerated concrete was investigated by in situ X-ray diffraction (XRD) analysis. High-energy X-rays from a synchrotron radiation source in combination with a newly developed autoclave cell and a photon-counting pixel array detector were used. To investigate the effects of the silica source, reactive quartz from chert and less-reactive quartz from quartz sand were used as starting materials. The effect of Al addition on tobermorite formation was also studied. In all cases, C-S-H, hydroxylellestadite and katoite were clearly observed as intermediates. Acceleration of tobermorite formation by Al addition was clearly observed. However, Al addition did not affect the dissolution rate of quartz. Two pathways, via C-S-H and katoite, were also observed in the Al-containing system. These results suggest that the structure of initially formed C-S-H is important for the subsequent tobermorite formation reactions.

  14. Formation of oxides of nitrogen in monodisperse spray combustion of hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Nizami, A. A.; Singh, S.; Cernansky, N. P.

    1982-01-01

    Experimental results of exit plane NO/NO(x) emissions from atmospheric monodisperse fuel spray combustion are presented. Six different hydrocarbon fuels were studied: isopropanol, n-propanol, n-octane, iso-octane, n-heptane and methanol. The results indicate an optimum droplet size for minimizing NO/NO(x) production for all of the test fuels. At the optimum droplet diameter, reductions in NO/NO(x) relative to the NO(x) occurred at droplet diameters of 55 and 48 microns respectively, as compared to a 50-micron droplet size for isopropanol. The occurrence of the minimum NO(x) point at different droplet diameters for the different fuels appears to be governed by the extent of prevaporization of the fuel in the spray, and is consistent with theoretical calculations based on each fuel's physical properties. Estimates are also given for the behavior of heavy fuels and of polydisperse fuel sprays in shifting the minimum NO(x) point compared to a monodisperse situation.

  15. 40 CFR 600.307-86 - Fuel economy label format requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy...) Catalyst usage, if necessary to distinguish otherwise identical model types; and (9) California emission control system usage, if applicable and if the Administrator determines that automobiles intended for...

  16. THE INFLUENCE OF CARBON BURNOUT ON SUBMICRON PARTICLE FORMATION FROM EMULSIFIED FUEL OIL COMBUSTION

    EPA Science Inventory

    The paper gives results of an examination of particle behavior and particle size distributions from the combustion of different fuel oils and emulsified fuels in three experimental combusators. Results indicate that improved carbon (C) burnout from fule oil combustion, either by...

  17. Effects of hypothermic storage of striped bass (Morone saxatilis) sperm on intracellular calcium, reactive oxygen species formation, mitochondrial function, motility, and viability

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experiments were conducted to determine the effect of hypothermic 24 h storage of striped bass sperm cells (Morone saxatilis) on viability, intracellular Ca2+ [Ca2+]i, mitochondrial membrane potential (''m), and reactive oxygen species (ROS) formation as determined by flow cytometry; motion activati...

  18. Effects of hypothermic storage of striped bass (Morone saxatilis) sperm on intracellular calcium, reactive oxygen species formation, mitochondrial function, motility, and viability

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experiments were conducted to determine the effect of hypothermic 24 h storage of striped bass sperm cells on viability, intracellular Ca2+ ([Ca2+]i), mitochondrial membrane potential (D'm), and reactive oxygen species (ROS) formation (oxidation of hydroethidine to ethidium) as determined by flow cy...

  19. Fuel effects on soot formation in turbojet engines. Final report, September 15, 1983-March 14, 1985

    SciTech Connect

    Gill, R.J.; Olson, D.B.

    1985-08-01

    The results of tests on how fuel composition affects the performance of three Navy aircraft engine combustors, the TF30, T56, and T53, were analyzed. The objective of this analysis was to identify which fuel property best correlated with the smoke-related measurements: radiation flux, liner temperature rise, smoke number, and smoke emissions. The effects of fuel composition were investigated by using a series of ten Naval Air Propulsion Center jet fuels with various properties, such as hydrogen contents of 12.83 to 13.82% and total aromatic hydrocarbon contents of 15.9 to 28.5%. Several laboratory combustion characteristics of these fuels were measured and these characteristics were used in analysis. Altogether, 15 fuel parameters were used to correlate the 45 combustor test results. The reported operating conditions of the tests, such as inlet air pressure, inlet air temperature, or fuel/air ratio, were also used as correlating parameters to determine whether variations in these variables, nearly constant for individual tests, also affected the smoke-related test results.

  20. Reduction of carbon dioxide gas formation at the anode of a direct methanol fuel cell using chemically enhanced solubility

    NASA Astrophysics Data System (ADS)

    Lundin, Michael D.; McCready, Mark J.

    The production of CO 2 gas at the DMFC anode leads to dramatic increases in pumping power requirements and reduced power output because of mass transfer limitations as bubble trains form in the channels of larger stacks. Experimental observations taken in a 5 cm 2 DMFC test cell operated at 60 °C, 1 atm, and with a methanol/water fuel flow rates of 5-10 cm 3 min -1 indicate that the rate of bubble formation can be reduced by increasing the fuel flow because more liquid is available for the CO 2 to dissolve in. Further observations indicate that KOH and LiOH added to the fuel eliminates CO 2 gas formation in situ at low concentrations because of the greatly increased solubility that results. A mathematical model for the volumetric rate of CO 2 gas production that includes effects of temperature and solubility is developed and extended to include the effects of hydroxide ions in solution. The model is used to predict the onset location of gas formation in the flow field as well as the void fraction at any point in the flow field. Predictions from the model agree very well with our experiments. Model predictions explain differences in the initial location of bubble formation for fuel solutions pre-saturated with CO 2 as opposed to CO 2-free solutions. Experiments with KOH and LiOH added to fuel solutions confirm the validity of the model extension that includes solubility that is enhanced by chemical reaction. Experiments with LiOH, KOH, and ammonium hydroxide show that the long-term durability of standard Pt-Ru/Nafion ®/Pt membrane electrode assemblies is compromised because of the presence of lithium, potassium, and ammonium cations that interact with the Nafion ® membrane and result in increasing the ohmic limitations of the polymer electrolyte membrane. Experiments with Ca(OH) 2, while reducing gas formation, precipitate the product CaCO 3 out of solution too rapidly for downstream filtering, blocking channels in the flow field.

  1. Using Reactive Transport Modeling to Understand Formation of the Stimson Sedimentary Unit and Altered Fracture Zones at Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Hausrath, E. M.; Ming, D. W.; Peretyazhko, T.; Rampe, E. B.

    2017-01-01

    Water flowing through sediments at Gale Crater, Mars created environments that were likely habitable, and sampled basin-wide hydrological systems. However, many questions remain about these environments and the fluids that generated them. Measurements taken by the Mars Science Laboratory Curiosity of multiple fracture zones can help constrain the environments that formed them because they can be compared to nearby associated parent material (Figure 1). For example, measurements of altered fracture zones from the target Greenhorn in the Stimson sandstone can be compared to parent material measured in the nearby Big Sky target, allowing constraints to be placed on the alteration conditions that formed the Greenhorn target from the Big Sky target. Similarly, CheMin measurements of the powdered < 150 micron fraction from the drillhole at Big Sky and sample from the Rocknest eolian deposit indicate that the mineralogies are strikingly similar. The main differences are the presence of olivine in the Rocknest eolian deposit, which is absent in the Big Sky target, and the presence of far more abundant Fe oxides in the Big Sky target. Quantifying the changes between the Big Sky target and the Rocknest eolian deposit can therefore help us understand the diagenetic changes that occurred forming the Stimson sedimentary unit. In order to interpret these aqueous changes, we performed reactive transport modeling of 1) the formation of the Big Sky target from a Rocknest eolian deposit-like parent material, and 2) the formation of the Greenhorn target from the Big Sky target. This work allows us to test the relationships between the targets and the characteristics of the aqueous conditions that formed the Greenhorn target from the Big Sky target, and the Big Sky target from a Rocknest eolian deposit-like parent material.

  2. Hydroxylated polychlorinated biphenyls increase reactive oxygen species formation and induce cell death in cultured cerebellar granule cells

    SciTech Connect

    Dreiem, Anne Rykken, Sidsel; Lehmler, Hans-Joachim; Robertson, Larry W.; Fonnum, Frode

    2009-10-15

    Polychlorinated biphenyls (PCBs) are persistent organic pollutants that bioaccumulate in the body, however, they can be metabolized to more water-soluble products. Although they are more readily excreted than the parent compounds, some of the metabolites are still hydrophobic and may be more available to target tissues, such as the brain. They can also cross the placenta and reach a developing foetus. Much less is known about the toxicity of PCB metabolites than about the parent compounds. In the present study, we have investigated the effects of eight hydroxylated (OH) PCB congeners (2'-OH PCB 3, 4-OH PCB 14, 4-OH PCB 34, 4'-OH PCB 35, 4-OH PCB 36, 4'-OH PCB 36, 4-OH PCB 39, and 4'-OH PCB 68) on reactive oxygen species (ROS) formation and cell viability in rat cerebellar granule cells. We found that, similar to their parent compounds, OH-PCBs are potent ROS inducers with potency 4-OH PCB 14 < 4-OH PCB 36 < 4-OH PCB 34 < 4'-OH PCB 36 < 4'-OH PCB 68 < 4-OH PCB 39 < 4'-OH PCB 35. 4-OH PCB 36 was the most potent cell death inducer, and caused apoptotic or necrotic morphology depending on concentration. Inhibition of ERK1/2 kinase with U0126 reduced both cell death and ROS formation, suggesting that ERK1/2 activation is involved in OH-PCB toxicity. The results indicate that the hydroxylation of PCBs may not constitute a detoxification reaction. Since OH-PCBs like their parent compounds are retained in the body and may be more widely distributed to sensitive tissues, it is important that not only the levels of the parent compounds but also the levels of their metabolites are taken into account during risk assessment of PCBs and related compounds.

  3. LIFE Materials: Phase Formation and Transformations in Transmutation Fuel Materials for the LIFE Engine Part I - Path Forward Volume 3

    SciTech Connect

    Turchi, P A; Kaufman, L; Fluss, M

    2008-12-19

    The current specifications of the LLNL fusion-fission hybrid proposal, namely LIFE, impose severe constraints on materials, and in particular on the nuclear fissile or fertile nuclear fuel and its immediate environment. This constitutes the focus of the present report with special emphasis on phase formation and phase transformations of the transmutation fuel and their consequences on particle and pebble thermal, chemical, and mechanical integrities. We first review the work that has been done in recent years to improve materials properties under the Gen-IV project, and with in particular applications to HTGR and MSR, and also under GNEP and AFCI in the USA. Our goal is to assess the nuclear fuel options that currently exist together with their issues. Among the options, it is worth mentioning TRISO, IMF, and molten salts. The later option will not be discussed in details since an entire report (Volume 8 - Molten-salt Fuels) is dedicated to it. Then, in a second part, with the specific LIFE specifications in mind, the various fuel options with their most critical issues are revisited with a path forward for each of them in terms of research, both experimental and theoretical. Since LIFE is applicable to very high burn-up of various fuels, distinctions will be made depending on the mission, i.e., energy production or incineration. Finally a few conclusions are drawn in terms of the specific needs for integrated materials modeling and the in depth knowledge on time-evolution thermo-chemistry that controls and drastically affects the performance of the nuclear materials and their immediate environment. Although LIFE demands materials that very likely have not yet been fully optimized, the challenges are not insurmountable, and a well concerted experimental-modeling effort should lead to dramatic advances that should well serve other fission programs such as Gen-IV, GNEP, AFCI as well as the international fusion program, ITER.

  4. Basin and range-age reactivation of the ancestral Rocky Mountains in Texas Panhandle: evidence from Ogallala Formation

    SciTech Connect

    Budnik, R.T.

    1984-04-01

    The Ogallala Formation (Neogene) is a widespread syntectonic alluvial apron that was shed eastward from the Rio Grande rift and related uplifts in Colorado and New Mexico during Basin and Range extension. In the Texas Panhandle, the Ogallala completely buried Ancestral Rocky Mountain (Pennsylvanian) structures. Renewed movement on these older structures during the Neogene influenced the thickness and facies distribution of the Ogallala. The Ogallala thickens into the Palo Duro, Dalhart, and Anadarko basins. Major distributary channels on Ogallala alluvial fans coincide with the axes of these basins, whereas major interchannel areas overlie intervening uplifts. Second-order structures subtly influenced the unit as well. For example, the Carson basin, a Pennsylvanian rhomb graben along the Amarillo uplift, the Ogallala is over 250 m (820 ft) thick compared with 90 m (275 ft) in adjacent areas. Within the Palo Duro basin, local highs controlled the distribution of thin, interchannel flood-basin and lacustrine deposits. Thicker, braided-stream channel deposits follow local lows. Later movement on the Amarillo uplift broadly folded the Ogallala. The southern high plains surface subtly reflects basement structure, with topographic highs overlying basement highs, suggesting post-Ogallala deformation within the Palo Duro basin. The Amarillo uplift is approximately perpendicular to the Rio Grande rift and parallel to the direction of Basin and Range extension. Thus, the stress field that produced the rift may have caused strike-slip movement and reactivation of the Carson basin along the Amarillo uplift.

  5. Role of nitrogen in the formation of hard and elastic CNx thin films by reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Hellgren, Niklas; Johansson, Mats P.; Broitman, Esteban; Hultman, Lars; Sundgren, Jan-Eric

    1999-02-01

    Carbon nitride films, deposited by reactive dc magnetron sputtering in Ar/N2 discharges, were studied with respect to composition, structure, and mechanical properties. CNx films, with 0<=x<=0.35, were grown onto Si (001) substrates at temperatures between 100 and 550 °C. The total pressure was kept constant at 3.0 mTorr with the N2 fraction varied from 0 to 1. As-deposited films were studied by Rutherford-backscattering spectroscopy, x-ray photoelectron spectroscopy, electron-energy loss spectroscopy, Raman and Fourier transform infrared spectroscopy, and nanoindentation. Three characteristic film structures could be identified: For temperatures below ~150 °C, an amorphous phase forms, the properties of which are essentially unaffected by the nitrogen concentration. For temperatures above ~200 °C, a transition from a graphitelike phase to a ``fullerenelike'' phase is observed when the nitrogen concentration increases from ~5 to ~15 at. %. This fullerenelike phase exhibits high hardness values and extreme elasticity, as measured by nanoindentation. A ``defected-graphite'' model, where nitrogen atoms goes into substitutional graphite sites, is suggested for explaining this structural transformation. When a sufficient number of nitrogen atoms is incorporated, formation of pentagons is promoted, leading to curving of the basal planes. This facilitates cross-linking between the planes and a distortion of the graphitic structure, and a strong three-dimensional covalently bonded network is formed.

  6. Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron

    NASA Technical Reports Server (NTRS)

    Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T.

    2002-01-01

    Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation.

  7. Investigation of spray dispersion and particulate formation in diesel fuel flames

    NASA Technical Reports Server (NTRS)

    Back, L. H.; Bankston, C. P.; Kwack, E. Y.; Bellan, J.; Harstad, K.

    1988-01-01

    An experimental study of electrostatical atomized and dispersed diesel fuel jets was conducted at various back pressures to 40 atm. A new electrostatic injection technique was utilized to generate continuous, stable fuel sprays at charge densities of 1.5 to 2.0 C/m3 of fluid at one atm, and about 1.0 C/m3 at 40 atm. Flowrates were varied from 0.5 to 2.5 ml/s and electric potentials to -18 kV. Visual observations showed that significant enhanced dispersion of charged fuel jets occurred at high back pressures compared to aerodynamic breakup and dispersion. The average drop size was about the same as the spray triode orifice diameter, and was between the Kelly theory and the Rayleigh limit. The ignition tests, done only at one atm, indicated stable combustion of the electrostatically dispersed fuel jets.

  8. Methods and apparatus for burning fuel with low NO[sub x] formation

    SciTech Connect

    Schwartz, R.E.; Waibel, R.T.; Rodden, P.M.; Napier, S.O.

    1992-10-13

    This patent describes an improved burner aparatus for discharging a mixture of fuel and air into a furnace space wherein the mixture is burned and flue gases having low NO[sub x] content are formed therefrom. It comprises: A housing; primary mixer-nozzle means; flue gases passageway means; at least one secondary fuel nozzel means. This patent also describes a method of discharging an at least substanitally stoichiometric mixture of fuel and air into a furnace wherein the mixture is burned and flue gases having low NO[sub x] content are formed therefrom. It comprises: discharging air into the furnace; discharging the remaining portion of the fuel into a secondary zone.

  9. Methods and apparatus for burning fuel with low NO sub x formation

    SciTech Connect

    Schwartz, R.E.; Waibel, R.T.; Rodden, P.M.; Napier, S.O.

    1992-03-24

    This patent describes an improved burner apparatus for discharging a mixture of fuel and air into a furnace space wherein the mixture is burned and flue gases having low NO{sub x} content are formed. It comprises: a housing having an open end attached to the furnace space; means for introducing a controlled quantity of air into the housing and into the furnace space attached to the housing; primary mixer-nozzle means for mixing fuel with flue gases from the furnace space and discharging the resulting mixture into the furnace space disposed within the housing, the primary mixer-nozzle means including a pressurized fuel inlet for connection to a source of pressurized fuel and at least one flue gases inlet connection.

  10. 40 CFR 600.307-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... vehicles, fuel cell vehicles, plug-in hybrid electric vehicles and vehicles equipped with hydrogen internal... hybrid electric vehicles. ...: minicompact cars may be “Minicompacts”, subcompact cars may be “Subcompacts”, compact cars may be...

  11. 40 CFR 600.307-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... vehicles, fuel cell vehicles, plug-in hybrid electric vehicles and vehicles equipped with hydrogen internal... hybrid electric vehicles. ...: minicompact cars may be “Minicompacts”, subcompact cars may be “Subcompacts”, compact cars may be...

  12. Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel.

    PubMed

    Duo, Wenli; Leclerc, Denys

    2007-04-01

    Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.

  13. ReaxFF reactive force field for solid oxide fuel cell systems with application to oxygen ion transport in yttria-stabilized zirconia.

    PubMed

    van Duin, Adri C T; Merinov, Boris V; Jang, Seung Soon; Goddard, William A

    2008-04-10

    We present the ReaxFF reactive force field developed to provide a first-principles-based description of oxygen ion transport through yttria-stabilized zirconia (YSZ) solid oxide fuel cell (SOFC) membranes. All parameters for ReaxFF were optimized to reproduce quantum mechanical (QM) calculations on relevant condensed phase and cluster systems. We validated the use of ReaxFF for fuel cell applications by using it in molecular dynamics (MD) simulations to predict the oxygen ion diffusion coefficient in yttria-stabilized zirconia as a function of temperature. These values are in excellent agreement with experimental results, setting the stage for the use of ReaxFF to model the transport of oxygen ions through the YSZ electrolyte for SOFC. Because ReaxFF descriptions are already available for some catalysts (e.g., Ni and Pt) and under development for other high-temperature catalysts, we can now consider fully first-principles-based simulations of the critical functions in SOFC, enabling the possibility of in silico optimization of these materials. That is, we can now consider using theory and simulation to examine the effect of materials modifications on both the catalysts and transport processes in SOFC.

  14. Primary emissions and secondary organic aerosol formation from the exhaust of a flex-fuel (ethanol) vehicle

    NASA Astrophysics Data System (ADS)

    Suarez-Bertoa, R.; Zardini, A. A.; Platt, S. M.; Hellebust, S.; Pieber, S. M.; El Haddad, I.; Temime-Roussel, B.; Baltensperger, U.; Marchand, N.; Prévôt, A. S. H.; Astorga, C.

    2015-09-01

    Incentives to use biofuels may result in increasing vehicular emissions of compounds detrimental to air quality. Therefore, regulated and unregulated emissions from a Euro 5a flex-fuel vehicle, tested using E85 and E75 blends (gasoline containing 85% and 75% of ethanol (vol/vol), respectively), were investigated at 22 and -7 °C over the New European Driving Cycle, at the Vehicle Emission Laboratory at the European Commission Joint Research Centre Ispra, Italy. Vehicle exhaust was comprehensively analyzed at the tailpipe and in a dilution tunnel. A fraction of the exhaust was injected into a mobile smog chamber to study the photochemical aging of the mixture. We found that emissions from a flex-fuel vehicle, fueled by E85 and E75, led to secondary organic aerosol (SOA) formation, despite the low aromatic content of these fuel blends. Emissions of regulated and unregulated compounds, as well as emissions of black carbon (BC) and primary organic aerosol (POA) and SOA formation were higher at -7 °C. The flex-fuel unregulated emissions, mainly composed of ethanol and acetaldehyde, resulted in very high ozone formation potential and SOA, especially at low temperature (860 mg O3 km-1 and up to 38 mg C kg-1). After an OH exposure of 10 × 106 cm-3 h, SOA mass was, on average, 3 times larger than total primary particle mass emissions (BC + POA) with a high O:C ratio (up to 0.7 and 0.5 at 22 and -7 °C, respectively) typical of highly oxidized mixtures. Furthermore, high resolution organic mass spectra showed high 44/43 ratios (ratio of the ions m/z 44 and m/z 43) characteristic of low-volatility oxygenated organic aerosol. We also hypothesize that SOA formation from vehicular emissions could be due to oxidation products of ethanol and acetaldehyde, both short-chain oxygenated VOCs, e.g. methylglyoxal and acetic acid, and not only from aromatic compounds.

  15. Cenosphere formation from heavy fuel oil: a numerical analysis accounting for the balance between porous shells and internal pressure

    NASA Astrophysics Data System (ADS)

    Reddy, Vanteru M.; Rahman, Mustafa M.; Gandi, Appala N.; Elbaz, Ayman M.; Schrecengost, Robert A.; Roberts, William L.

    2016-01-01

    Heavy fuel oil (HFO) as a fuel in industrial and power generation plants ensures the availability of energy at economy. Coke and cenosphere emissions from HFO combustion need to be controlled by particulate control equipment such as electrostatic precipitators, and collection effectiveness is impacted by the properties of these particulates. The cenosphere formation is a function of HFO composition, which varies depending on the source of the HFO. Numerical modelling of the cenosphere formation mechanism presented in this paper is an economical method of characterising cenosphere formation potential for HFO in comparison to experimental analysis of individual HFO samples, leading to better control and collection. In the present work, a novel numerical model is developed for understanding the global cenosphere formation mechanism. The critical diameter of the cenosphere is modelled based on the balance between two pressures developed in an HFO droplet. First is the pressure (Prpf) developed at the interface of the liquid surface and the inner surface of the accumulated coke due to the flow restriction of volatile components from the interior of the droplet. Second is the pressure due to the outer shell strength (PrC) gained from van der Walls energy of the coke layers and surface energy. In this present study it is considered that when PrC ≥ Prpf the outer shell starts to harden. The internal motion in the shell layer ceases and the outer diameter (DSOut) of the shell is then fixed. The entire process of cenosphere formation in this study is analysed in three phases: regression, shell formation and hardening, and post shell hardening. Variations in pressures during shell formation are analysed. Shell (cenosphere) dimensions are evaluated at the completion of droplet evaporation. The rate of fuel evaporation, rate of coke formation and coke accumulation are analysed. The model predicts shell outer diameters of 650, 860 and 1040 µm, and inner diameters are 360, 410

  16. Basic combustion and pollutant-formation processes for pulverized fuels. Quarterly technical progress report No. 4, 1 July 1981-30 September 1981

    SciTech Connect

    Germane, G.J.; Smoot, L.D.

    1981-10-15

    This contract study of basic combustion and pollutant formation processes for pulverized solid fossil fuels includes coal-water mixtures and chars derived from coal pyrolysis, liquefaction or gasification processes. The factors that affect the physical properties of coal-water mixtures (CWM) have been identified and characterization tests initiated to determine how these variables (e.g., solids loading, particle size, particle size distribution, additives) affect the coal slurries. A bench-scale apparatus consisting of a pressure vessel and an atomizing nozzle was designed and is being fabricated. This apparatus will assist in the development of handling and atomization techniques for the combustion tests. It will also aid in comparing viscosities of slurries of different solids loadings and coal types. Chars were obtained for characterization tests. A series of potential tests to characterize the chars was identified. Grading and sizing of the chars was begun as well as elemental analysis. Samples of the chars were sent to Phillips for CO/sub 2/ reactivity tests to be performed. Coding for incorporation of swirling flows into the two-dimensional coal combustion model (PCGC-2) was completed. Debugging was initiated and sample computations are performed for a gaseous, isothermal system for low swirl numbers. Convergence problems were encountered when attempts were made to complete runs at higher swirl numbers.

  17. In situ formation of leak-free polyethylene glycol (PEG) membranes in microfluidic fuel cells.

    PubMed

    Ho, W F; Lim, K M; Yang, K-L

    2016-11-29

    Membraneless microfluidic fuel cells operated under two co-laminar flows often face serious fuel cross-over problems, especially when flow rates are close to zero. In this study, we show that polyethylene glycol (PEG) monomers can be cross-linked inside microfluidic channels to form leak-free PEG membranes, which prevent mixing of two incompatible electrolyte solutions while allowing diffusion of certain molecules (e.g. glucose) and ions. By using PEG monomers of different molecular weights and cross-linking conditions, we are able to tailor selectivity of the membrane to allow passage of glucose while blocking larger molecules such as trypan blue. As a proof of principle, a microfluidic fuel cell with a PEG membrane and two incompatible electrolytes (acid and base) is demonstrated. Thanks to the leak-free nature of the PEG membrane, these two electrolytes do not mix together even at very slow flow rates. This microfluidic fuel cell is able to generate a voltage up to ∼450 mV from 10 mM of glucose with a flow rate of 20 μL min(-1). This microfluidic fuel cell is potentially useful as a miniature power source for many applications.

  18. The study of alternate, solid-phase fluorinating agents for use in reactive gas recycle of used nuclear fuel

    NASA Astrophysics Data System (ADS)

    Inabinett, Dillon

    Surrogate oxides of the Used Nuclear Fuel (UNF) matrix were fluorinated using alternate, solid-phase fluorinating agents XeF2 and NH4HF2 to form volatile and non-volatile compounds and demonstrate the possibility of a chemical and thermal separations. A matrix of experiments was conducted at the milligram quantity scale using a Shimadzu DTG-60 TG/DTA installed at SRNL (Savannah River National Laboratory) for testing of all non-radioactive samples and a Netzsch STA 409 TGA installed in the laboratory at USC (University of South Carolina) for testing of all radioactive samples. The fluorination and subsequent volatilization potentials were analyzed by mixing excess fluorinating agent with a surrogate oxide at roughly a 2:1 ratio and then heated to elevated temperatures for analysis. Thermogravimetric and differential thermal analysis allowed for reaction pathways to be analyzed and suggest windows both thermally and chemically for separations of these various components. The differences in thermophysical properties of these products can be utilized as a starting point to effectively separate, isolate, and collect product streams with different product composition for further processing. The study of these chemistries could be incorporated into advanced separations methods to provide another possible solution for the long-term sustainability of nuclear power as the issue of reuse and disposal of commercial fuel continues to grow.

  19. Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species.

    PubMed

    Corona, Teresa; Pfaff, Florian F; Acuña-Parés, Ferran; Draksharapu, Apparao; Whiteoak, Christopher J; Martin-Diaconescu, Vlad; Lloret-Fillol, Julio; Browne, Wesley R; Ray, Kallol; Company, Anna

    2015-10-12

    Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a Ni(II) precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., C-H bonds, C=C bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic O-O bond cleavage of a Ni-HmCPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a Ni(III) -oxyl compound.

  20. Formation of plagioclase-bearing peridotite and plagioclase-bearing wehrlite and gabbro suite through reactive crystallization: an experimental study

    NASA Astrophysics Data System (ADS)

    Saper, Lee; Liang, Yan

    2014-03-01

    Plagioclase-bearing peridotites are commonly associated with gabbroic rocks sampled around the Moho Transition Zone. Based on mineral chemistry, texture, and spatial relations, the formation of plagioclase-bearing peridotites has been attributed to impregnation of basalt into residual peridotites. We conducted reactive dissolution and crystallization experiments to test this hypothesis by reacting a primitive mid-ocean ridge basalt with a melt-impregnated lherzolite at 1,300 °C and 1 GPa and then cooling to 1,050 °C as pressure decreased to 0.7 GPa. Crystallization during cooling produced lithologic sequences of gabbro-wehrlite or gabbro-wehrlite-peridotite, depending on reaction time. Wehrlitic and peridotitic sections contain significant amounts of plagioclase interstitial to olivine and clinopyroxene and plagioclase compositions are spatially homogeneous. Clinopyroxene in the wehrlite-peridotite section is reprecipitated from the melt and exhibits poikilitic texture with small rounded olivine chadacrysts. Mineral composition in olivine and clinopyroxene varies spatially, both at the scale of the sample and within individual grains. Olivine grains that crystallized close to the melt-peridotite interface are enriched in iron due to their proximity to the basaltic melt reservoir. Consistent with many field studies, we observed gradual spatial variation in olivine and clinopyroxene composition across a lithologically sharp boundary between the gabbro and wehrlite-peridotite. Plagioclase compositions show no obvious dependence on distance from the melt-rock interface and were precipitated from late-stage trapped melts. Compositional trends of olivine, pyroxene, and plagioclase are consistent with previous experimental results and natural observations of the Moho Transition Zone. Different lithological sequences form based primarily on the melt-rock ratio, composition of the melt and host peridotite, and thermochemical conditions, but are expected to grade from

  1. Basic combustion and pollutant-formation processes for pulverized fuels. Quarterly technical progress report No. 1, 1 October 1980-31 December 1980

    SciTech Connect

    Germane, Geoffery J.; Smoot, L. Douglas

    1981-01-15

    A study of basic combustion and pollutant formation processes for pulverized solid fossil fuels has been initiated. The solid fossil fuels under consideration for this research include such solid fuels as non-bituminous coal types, solvent refined coal, combustion char, petroleum coke, oil shale and tar sand. The potential industrial application of pulverized fuels other than coal provides some promise for relief from present and future conventional fuel shortages. Utilization problems with these fuels such as flame stability, fuel handling, pollutant emission and ash and slag formation in large-scale furnaces may be fundamentally addressed in laboratory reactors using properly scaled operating variables. An extensive literature search was begun to assess current knowledge relative to utilization of these fuels. This review will provide a basis for selection of three solid fuels for testing. Pertinent information from industrial contacts will also be used in the fuel selection. The criteria to be used in the selection of these fuels include availability for economic industrial use, adaptability, grindability, flame stability, entrainability, uniformity, applicability to direct firing with air, solidity with heating, availability to the BYU Combustion Laboratory, cost, other physical characteristics affecting their use, industrial input and recommendations, and DOE approval. The existing laboratory coal combustor at BYU will be modified to provide flexibility for a potentially wide range of operating characteristics with the selected solid fuels. A computer system has been identified for interface both to the reactor for data acquisition and control of operating variables and to the main research computer for final data reduction and display.

  2. Cryogenic hydrogen fuel for controlled inertial confinement fusion (formation of reactor-scale cryogenic targets)

    NASA Astrophysics Data System (ADS)

    Aleksandrova, I. V.; Koresheva, E. R.; Krokhin, O. N.; Osipov, I. E.

    2016-12-01

    In inertial fusion energy research, considerable attention has recently been focused on low-cost fabrication of a large number of targets by developing a specialized layering module of repeatable operation. The targets must be free-standing, or unmounted. Therefore, the development of a target factory for inertial confinement fusion (ICF) is based on methods that can ensure a cost-effective target production with high repeatability. Minimization of the amount of tritium (i.e., minimization of time and space at all production stages) is a necessary condition as well. Additionally, the cryogenic hydrogen fuel inside the targets must have a structure (ultrafine layers—the grain size should be scaled back to the nanometer range) that supports the fuel layer survivability under target injection and transport through the reactor chamber. To meet the above requirements, significant progress has been made at the Lebedev Physical Institute (LPI) in the technology developed on the basis of rapid fuel layering inside moving free-standing targets (FST), also referred to as the FST layering method. Owing to the research carried out at LPI, unique experience has been gained in the development of the FST-layering module for target fabrication with an ultrafine fuel layer, including a reactor- scale target design. This experience can be used for the development of the next-generation FST-layering module for construction of a prototype of a target factory for power laser facilities and inertial fusion power plants.

  3. FINE PARTICLE EMISSIONS FROM RESIDUAL FUEL OIL COMBUSTION: CHARACTERIZATION AND MECHANISMS OF FORMATION

    EPA Science Inventory

    The paper gives results of a comparison of the characteristics of particulate matter (PM) emitted from residual fuel oil combustion in two types of combustion equipment. A small commercial 732-kW-rated fire-tube boiler yielded a weakly bimodal PM size distribution (PSD) with over...

  4. FINE PARTICLE EMISSIONS FROM RESIDUAL FUEL OIL COMBUSTION: CHARACTERIZATION AND MECHANISMS OF FORMATION

    EPA Science Inventory

    The paper gives results of a comparison of the characteristics of particulate matter (PM) emitted from residual fuel oil combustion in two types of combustion equipment. A small commercial 732-kW fire-tube boiler yielded a weakly bi-modal particulate size distribution (PSD) with...

  5. 3,3'-Dihydroxyisorenieratene prevents UV-induced formation of reactive oxygen species and the release of protein-bound zinc ions in human skin fibroblasts.

    PubMed

    Lutter, Kaya; De Spirt, Silke; Kock, Sebastian; Kröncke, Klaus-Dietrich; Martin, Hans-Dieter; Wagener, Tanja; Stahl, Wilhelm

    2010-02-01

    3,3'-Dihydroxyisorenieratene (DHIR) is a structurally unusual carotenoid exhibiting bifunctional antioxidant properties. It is synthesized by Brevibacterium linens, used in dairy industry for the production of red smear cheeses. The compound protects cellular structures against photo-oxidative damage and inhibits the UV-dependent formation of thymidine dimers. Here we show that DHIR prevents a UV-induced intracellular release of zinc ions from proteins in human dermal fibroblasts. The effect is correlated with a decreased formation of intracellular reactive oxygen species. In contrast, zinc release from cellular proteins induced by hyperthermia is not affected by pretreatment of cells with the antioxidant DHIR. It is suggested that the intracellular zinc release upon UV irradiation is due to oxidative modifications of the zinc ligands in proteins (e.g. cysteine) and that protection by DHIR is due to intracellular scavenging of reactive oxygen species generated in photo-oxidation.

  6. Reactivity of niobium-carbon cluster ions with hydrogen molecules in relation to formation mechanism of Met-Car cluster ions.

    PubMed

    Miyajima, Ken; Fukushima, Naoya; Mafuné, Fumitaka

    2008-07-03

    It is known that a niobium-carbon Met-Car cluster ion (Nb 8C 12 (+)) and its intermediates (Nb 4C 4 (+), Nb 6C 7 (+), etc.) are selectively formed by the aggregation of the Nb atoms in the presence of hydrocarbons. To elucidate the formation mechanism, we prepared Nb n C m (+) with every combination of n and m in the gas phase by the laser vaporization technique. The reactivity of Nb n C m (+) with H 2 was examined under the multiple collision condition, finding that Nb n C m (+) between Nb 2C 3 (+) and Nb 8C 12 (+) are not reactive with H 2. On the basis of the H 2 affinity of Nb n C m (+) experimentally obtained, we propose a dehydrogenation-controlled formation mechanism of niobium-carbon Met-Car cluster ions.

  7. Tuning reactivity of glycosyl imidinium intermediate for 2-azido-2-deoxyglycosyl donors in α-glycosidic bond formation.

    PubMed

    Ingle, Arun B; Chao, Chin-Sheng; Hung, Wei-Cheng; Mong, Kwok-Kong Tony

    2013-10-18

    The chemical properties of nucleophile additives were investigated in a modulated glycosylation context. N-Formylmorpholine (NFM) was found to be an effective modulator for glycosylation with less reactive 2-azido-2-deoxythioglucosyl and thiogalactosyl donors.

  8. Nano composite membrane-electrode assembly formation for fuel cell-modeling aspects

    NASA Astrophysics Data System (ADS)

    Vaivars, G.; Linkov, V.

    2007-12-01

    Long term stability is an essential requirement for fuel cell applications in automobile and stationary energy systems. In these systems the agglomeration of the catalyst nanoparticles is a well-known phenomenon which cannot be easily overcome or compensated for by re-designing the system. A direct result of this occurrence is the irreversible decrease of the electrochemical performance. Irregularities in electric field distribution are one root cause for migration and subsequent agglomeration of the catalyst nanoparticle. In this work, the impact of the electrode mechanical deformation on electric field distribution was studied using a computer modeling approach. Model of a Proton Exchange Membrane (PEM) fuel cell with interdigitated flow field from Comsol Chemical Engineering/Electrochemical Engineering Module library was used for simulations. It was established that by minimizing the backing layer deformation it is possible to achieve some improvement in current distribution.

  9. Deposit formation in hydrocarbon rocket fuels with an evaluation of a propane heat transfer correlation

    NASA Technical Reports Server (NTRS)

    Masters, P. A.; Aukerman, C. A.

    1982-01-01

    A high pressure fuel coking testing apparatus was designed and developed and was used to evaluate thermal decomposition limits and carbon decomposition rates in heated copper tubes for hydrocarbon fuels. A commercial propane (90% grade) and chemically pure (CP) propane were tested. Heat transfer to supercritical propane was evaluated at 136 atm, bulk fluid velocities of 6 to 30 m/s, and tube wall temperatures in the range of 422 to 811 K. A forced convection heat transfer correlation developed in a previous test effort verified a prediction of most of the experimental data within a + or - 30% range, with good agreement for the CP propane data. No significant differences were apparent in the predictions derived from the correlation when the carbon resistance was included with the film resistance. A post-test scanning electron microprobe analysis indicated occurrences of migration and interdiffusion of copper into the carbon deposit.

  10. Experimental investigation of homogeneous charge compression ignition combustion of biodiesel fuel with external mixture formation in a CI engine.

    PubMed

    Ganesh, D; Nagarajan, G; Ganesan, S

    2014-01-01

    In parallel to the interest in renewable fuels, there has also been increased interest in homogeneous charge compression ignition (HCCI) combustion. HCCI engines are being actively developed because they have the potential to be highly efficient and to produce low emissions. Even though HCCI has been researched extensively, few challenges still exist. These include controlling the combustion at higher loads and the formation of a homogeneous mixture. To obtain better homogeneity, in the present investigation external mixture formation method was adopted, in which the fuel vaporiser was used to achieve excellent HCCI combustion in a single cylinder air-cooled direct injection diesel engine. In continuation of our previous works, in the current study a vaporised jatropha methyl ester (JME) was mixed with air to form a homogeneous mixture and inducted into the cylinder during the intake stroke to analyze the combustion, emission and performance characteristics. To control the early ignition of JME vapor-air mixture, cooled (30 °C) Exhaust gas recirculation (EGR) technique was adopted. The experimental result shows 81% reduction in NOx and 72% reduction in smoke emission.

  11. Fine Particle Emissions from Residual Fuel Oil Combustion: Characterization and Mechanisms of Formation

    DTIC Science & Technology

    2000-08-04

    NC, 1999. 3 . Bachmann, J. D ., Damberg, R. J., Caldwell, J. C., Ed- wards, C., and Koman, P. D ., Review of the National Ambient Air Quality Standards...residual fuel oil combustion to be suspect, as far as emission of toxic fine particles is concerned. Build- ing upon previous work examining the...control number. 1. REPORT DATE 04 AUG 2000 2. REPORT TYPE N/A 3 . DATES COVERED - 4. TITLE AND SUBTITLE Fine Particle Emissions from Residual

  12. Ozone uptake and formation of reactive oxygen intermediates on glassy, semi-solid and liquid organic matter

    NASA Astrophysics Data System (ADS)

    Berkemeier, Thomas; Steimer, Sarah S.; Krieger, Ulrich K.; Peter, Thomas; Pöschl, Ulrich; Ammann, Markus; Shiraiwa, Manabu

    2016-04-01

    Heterogeneous and multiphase reactions of ozone are important pathways for chemical ageing of atmospheric organic aerosols (Abbatt, Lee and Thornton, 2012). The effects of particle phase state on the reaction kinetics are still not fully elucidated and cannot be described by classical models assuming a homogeneous condensed phase (Berkemeier et al., 2013). We apply a kinetic multi-layer model, explicitly resolving gas adsorption, condensed phase diffusion and condensed phase chemistry (Shiraiwa et al., 2010), to systematic measurements of ozone uptake onto proxies for secondary organic aerosols (SOA). Our findings show how moisture-induced phase changes affect the gas uptake and chemical transformation of organic matter through change in the physicochemical properties of the substrate: the diffusion coefficients are found to be low under dry conditions, but increase by several orders of magnitude toward higher relative humidity (RH). The solubility of ozone in the dry organic matrix is found to be one order of magnitude higher than in the dilute aqueous solution. The model simulations reveal that at high RH, ozone uptake is mainly controlled by reaction throughout the particle bulk, whereas at low RH, bulk diffusion is retarded severely and reaction at the surface becomes the dominant pathway, with ozone uptake being limited by replenishment of unreacted organic molecules from the bulk phase. The experimental results can only be reconciled including a pathway for ozone self-reaction, which becomes especially important under dry and polluted conditions. Ozone self-reaction can be interpreted as formation and recombination of long-lived reactive oxygen intermediates at the aerosol surface, which could also explain several kinetic parameters and has implications for the health effects of organic aerosol particles. This study hence outlines how kinetic modelling can be used to gain mechanistic insight into the coupling of mass transport, phase changes, and chemical

  13. Quantitative Surface Emissivity and Temperature Measurements of a Burning Solid Fuel Accompanied by Soot Formation

    NASA Technical Reports Server (NTRS)

    Piltch, Nancy D.; Pettegrew, Richard D.; Ferkul, Paul; Sacksteder, K. (Technical Monitor)

    2001-01-01

    Surface radiometry is an established technique for noncontact temperature measurement of solids. We adapt this technique to the study of solid surface combustion where the solid fuel undergoes physical and chemical changes as pyrolysis proceeds, and additionally may produce soot. The physical and chemical changes alter the fuel surface emissivity, and soot contributes to the infrared signature in the same spectral band as the signal of interest. We have developed a measurement that isolates the fuel's surface emissions in the presence of soot, and determine the surface emissivity as a function of temperature. A commercially available infrared camera images the two-dimensional surface of ashless filter paper burning in concurrent flow. The camera is sensitive in the 2 to 5 gm band, but spectrally filtered to reduce the interference from hot gas phase combustion products. Results show a strong functional dependence of emissivity on temperature, attributed to the combined effects of thermal and oxidative processes. Using the measured emissivity, radiance measurements from several burning samples were corrected for the presence of soot and for changes in emissivity, to yield quantitative surface temperature measurements. Ultimately the results will be used to develop a full-field, non-contact temperature measurement that will be used in spacebased combustion investigations.

  14. Deuterium-Tritium Fuel Layer Formation for the National Ignition Facility

    SciTech Connect

    Kozioziemski, B. J.; Mapoles, E. R.; Sater, J. D.; Chernov, A. A.; Moody, J. D.; Lugten, J. B.; Johnson, M. A.

    2011-01-01

    Inertial confinement fusion requires very smooth and uniform solid deuterium-tritium (D-T) fuel layers. The National Ignition Facility (NIF) point design calls for a 65- to 75-m-thick D-T fuel layer inside of a 2-mm-diam spherical ablator shell to be 1.5 K below the D-T melting temperature (Tm) of 19.79 K. We also find that the layer quality depends on the initial crystal seeding, with the best layers grown from a single seed. The low modes of the layer are controlled by thermal shimming of the hohlraum and meet the NIF requirement with beryllium shells and nearly meet the requirement with plastic shells. The remaining roughness is localized in grain-boundary grooves and is minimal for a single crystal layer. Once formed, the layers need to be cooled to Tm - 1.5 K. Here, we studied dependence of the roughness on the cooling rate and found that cooling at rates of 0.03 to 0.5 K/s is able to preserve the layer structure for a few seconds after reaching the desired temperature. The entire fuel layer remains in contact with the shell during this rapid cooling. Therefore, rapid cooling of the layers is able to satisfy the NIF ignition requirements.

  15. A highly efficient immobilized ZnO/Zn photoanode for degradation of azo dye Reactive Green 19 in a photocatalytic fuel cell.

    PubMed

    Lee, Sin-Li; Ho, Li-Ngee; Ong, Soon-An; Wong, Yee-Shian; Voon, Chun-Hong; Khalik, Wan Fadhilah; Yusoff, Nik Athirah; Nordin, Noradiba

    2017-01-01

    Photocatalytic fuel cell (PFC) is a potential wastewater treatment technology that can generate electricity from the conversion of chemical energy of organic pollutants. An immobilized ZnO/Zn fabricated by sonication and heat attachment method was applied as the photoanode and Pt/C plate was used as the cathode of the PFC in this study. Factors that affect the decolorization efficiency and electricity generation of the PFC such as different initial dye concentrations and pH were investigated. Results revealed that the degradation of Reactive Green 19 (RG19) was enhanced in a closed circuit PFC compared with that of a opened circuit PFC. Almost 100% decolorization could be achieved in 8 h when 250 mL of 30 mg L(-1) of RG19 was treated in a PFC without any supporting electrolyte. The highest short circuit current of 0.0427 mA cm(-2) and maximum power density of 0.0102 mW cm(-2) was obtained by PFC using 30 mg L(-1) of RG19. The correlation between dye degradation, conductivity and voltage output were also investigated and discussed.

  16. Simulated Performance of the Integrated Passive Neutron Albedo Reactivity and Self-Interrogation Neutron Resonance Densitometry Detector Designed for Spent Fuel Measurement at the Fugen Reactor in Japan

    SciTech Connect

    Ulrich, Timothy J. II; Lafleur, Adrienne M.; Menlove, Howard O.; Swinhoe, Martyn T.; Tobin, Stephen J.; Seya, Michio; Bolind, Alan M.

    2012-07-16

    An integrated nondestructive assay instrument, which combined the Passive Neutron Albedo Reactivity (PNAR) and the Self-Interrogation Neutron Resonance Densitometry (SINRD) techniques, is the research focus for a collaborative effort between Los Alamos National Laboratory (LANL) and the Japanese Atomic Energy Agency as part of the Next Generation Safeguard Initiative. We will quantify the anticipated performance of this experimental system in two physical environments: (1) At LANL we will measure fresh Low Enriched Uranium (LEU) assemblies for which the average enrichment can be varied from 0.2% to 3.2% and for which Gd laced rods will be included. (2) At Fugen we will measure spent Mixed Oxide (MOX-B) and LEU spent fuel assemblies from the heavy water moderated Fugen reactor. The MOX-B assemblies will vary in burnup from {approx}3 GWd/tHM to {approx}20 GWd/tHM while the LEU assemblies ({approx}1.9% initial enrichment) will vary from {approx}2 GWd/tHM to {approx}7 GWd/tHM. The estimated count rates will be calculated using MCNPX. These preliminary results will help the finalization of the hardware design and also serve a guide for the experiment. The hardware of the detector is expected to be fabricated in 2012 with measurements expected to take place in 2012 and 2013. This work is supported by the Next Generation Safeguards Initiative, Office of Nuclear Safeguards and Security, National Nuclear Security Administration.

  17. Effects of sludge retention times on reactivity of effluent dissolved organic matter for trihalomethane formation in hybrid powdered activated carbon membrane bioreactors.

    PubMed

    Ma, Defang; Gao, Baoyu; Xia, Chufan; Wang, Yan; Yue, Qinyan; Li, Qian

    2014-08-01

    In this study, real municipal wastewater intended for reuse was treated by two identical hybrid PAC/MBRs (membrane bioreactors with powdered activated carbon addition), which were operated at sludge retention times (SRTs) of 30 and 180 days, respectively. In order to investigate the effects of SRT on trihalomethane (THM) formation in chlorinated PAC/MBR effluents, characteristics and THM formation reactivity of effluent dissolved organic matter (EfOM) at different SRTs were examined. PAC/MBR-180 had higher level of EfOM, which contained less simple aromatic proteins and exhibited lower specific UV absorbance. EfOM with molecular weight <5 kDa from PAC/MBR-30 (23%) was lower than PAC/MBR-180 (26%). About 50% of EfOM from PAC/MBR-30 was hydrophobic acids, which was higher than that from PAC/MBR-180 (about 36%). EfOM at SRT 180 days exhibited higher hydrophilicity. Prolonging SRT greatly reduced THM formation reactivity of EfOM, but increased the formation of bromine-containing species during chlorination of PAC/MBR effluents.

  18. Effects of diesel fuel combustion-modifier additives on In-cylinder soot formation in a heavy-duty Dl diesel engine.

    SciTech Connect

    Musculus, Mark P. (Sandia National Laboratories, Livermore, CA); Dietz, Jeff

    2005-07-01

    Based on a phenomenological model of diesel combustion and pollutant-formation processes, a number of fuel additives that could potentially reduce in-cylinder soot formation by altering combustion chemistry have been identified. These fuel additives, or ''combustion modifiers'', included ethanol and ethylene glycol dimethyl ether, polyethylene glycol dinitrate (a cetane improver), succinimide (a dispersant), as well as nitromethane and another nitro-compound mixture. To better understand the chemical and physical mechanisms by which these combustion modifiers may affect soot formation in diesel engines, in-cylinder soot and diffusion flame lift-off were measured, using an optically-accessible, heavy-duty, direct-injection diesel engine. A line-of-sight laser extinction diagnostic was employed to measure the relative soot concentration within the diesel jets (''jetsoot'') as well as the rates of deposition of soot on the piston bowl-rim (''wall-soot''). An OH chemiluminescence imaging technique was utilized to measure the lift-off lengths of the diesel diffusion flames so that fresh oxygen entrainment rates could be compared among the fuels. Measurements were obtained at two operating conditions, using blends of a base commercial diesel fuel with various combinations of the fuel additives. The ethanol additive, at 10% by mass, reduced jet-soot by up to 15%, and reduced wall-soot by 30-40%. The other fuel additives also affected in-cylinder soot, but unlike the ethanol blends, changes in in-cylinder soot could be attributed solely to differences in the ignition delay. No statistically-significant differences in the diesel flame lift-off lengths were observed among any of the fuel additive formulations at the operating conditions examined in this study. Accordingly, the observed differences in in-cylinder soot among the fuel formulations cannot be attributed to differences in fresh oxygen entrainment upstream of the soot-formation zones after ignition.

  19. Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

    NASA Astrophysics Data System (ADS)

    Bligh, Mark W.; Waite, T. David

    2011-12-01

    Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were

  20. SPATIAL AND TEMPORAL TRENDS IN GROUNDWATER CHEMISTRY AND PRECIPITATE FORMATION AT THE ELIZABETH CITY PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    Accumulation of mineral precipitates and microbial biomass are key factors that impact the long-term performance of PRBs. Both processes can impact remedial performance by affecting zero-valent iron reactivity and permeability. Results will be presented from solid-phase and gro...

  1. Scale formation on Ni-based alloys in simulated solid oxide fuel cell interconnect environments

    SciTech Connect

    Ziomek-Moroz, Margaret; Cramer, Stephen D.; Holcomb, Gordon R.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Singh, P.; Windisch, C.F.; Johnson, C.D.; Schaeffer, C.

    2004-11-01

    Recent publications suggest that the environment on the fuel side of the bi-polar stainless steel SOFC interconnects changes the oxidation behavior and morphology of the scale formed on the air side. The U.S. Department of Energy Albany Research Center (ARC), has examined the role of such exposure conditions on advanced nickel base alloys. Alloy formulations developed at ARC and commercial alloys were studied using X-ray diffraction (XRD) and Raman spectroscopy. The electrical property of oxide scales formed on selected alloys was determined in terms of areaspecific resistance (ASR). The corrosion behavior of ARC nickel-based alloys exposed to a dual environment of air/ H2 were compared to those of Crofer 22APU and Haynes 230.

  2. Carbon monoxide formation in UO2 kerneled HTR fuel particles containing oxygen getters

    NASA Astrophysics Data System (ADS)

    Proksch, E.; Strigl, A.; Nabielek, H.

    1986-01-01

    Mass spectrometric measurements of CO in irradiated UO2 fuel particles containing oxygen getters are summarized. Uranium carbide addition in the 3% to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, ambiguous results are obtained; ZrC probably results in CO reduction by a factor of 40; Ce2O3 and La2O3 seem less effective than the carbides; for Ce2O3, reduction factors between 3 and 15 are found. However, the results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO2 + Al2O3 has no influence on CO release.

  3. Examination of Mechanisms and Fuel-Molecular Effects on Soot Formation.

    DTIC Science & Technology

    1986-12-10

    t.’c. styrene, 1,3,5-hexatriene, biazeyl s--c 19I ABSTRACT iCantsaag onu ,vpee it n~emtpgi and Idmenty Opy biack numbgri * A an .:roaon as beer ...0.0175 C H/C H * 3.3/0.51 .2 2/7H8 Acetaldehyde , CH CHO * 0.105 5’ 3 All fuels were diluted in argon and (except for the experiments on pure toluene...0o2 3.3/2.05 C 2H4/02 0.22/0.13 1,3,5-Hexatriene, C6 H8 1.0 1,3,5-Hexatriene, C6 H8 0.09 Acetaldehyde , CH 3CHO * 0.01 Biacetyl, (CH 3 CO) 2 * 0.22

  4. Experimental study of soot formation from a diesel fuel surrogate in a shock tube

    SciTech Connect

    Mathieu, Olivier; Djebaili-Chaumeix, Nabiha; Paillard, Claude-Etienne; Douce, Francoise

    2009-08-15

    The soot tendency (soot induction delay time and soot yield) of a diesel fuel surrogate and of the hydrocarbons that constitute this mixture was studied in a heated shock tube. The surrogate is composed of three hydrocarbons representative of major chemical families of diesel fuels (39% n-propylcyclohexane, 28% n-butylbenzene, and 33% 2,2,4,4,6,8,8-heptamethylnonane in mass proportion). Experiments were carried out for highly diluted mixtures in argon; in the case of pyrolysis and at two equivalence ratios: 18 and 5. The pressure range was relatively high (1090-1870 kPa) and the carbon atom concentration was kept constant at around 2 x 10{sup +18} atoms cm{sup -3}. The effects of the nature of the hydrocarbon, the oxygen addition, and the temperature on the soot induction delay time and soot yield were investigated. A second growth stage of the soot volume fraction was observed. The influence of several parameters on the existence and/or on the amplitude of this second growth seems to indicate the chemical nature of this phenomenon. Results for the soot tendency show that the soot induction delay time and soot yield depend strongly on the structure of the hydrocarbon and on the concentration of oxygen. The study of the diesel surrogate shows that the soot inception process does not depend on synergistic effects between hydrocarbons but seems to be initiated by the constituent of the surrogate that produces soot fastest, while other constituents were consumed later during the soot growth. (author)

  5. Pollutant formation and emissions from cement kiln stack using a solid recovered fuel from municipal solid waste.

    PubMed

    Conesa, Juan A; Rey, Lorena; Egea, Silvia; Rey, Maria D

    2011-07-01

    The thermal decomposition of a solid recovered fuel (SRF) has been studied by two techniques. First, laboratory-scale experiments were performed in a horizontal furnace in which different atmospheres were studied to analyze the dioxins and furans (PCDD/Fs) evolved from the decomposition of the material. Sulfur presence was revealed to be important in PCDD/Fs formation. In the second technique, the emissions of various pollutants (PAHs, PCDD/Fs, metals, acid gases, etc.) were determined in a cement kiln fed on different proportions of SRF material, and where a maximum feed rate of 15000 kg SRF/h was achieved. In the laboratory furnace the dioxin toxicity revealed a maximum when the amount of oxygen in the atmosphere increased until approximately stoichiometric conditions. In the cement kiln, all emitted pollutants were under the legal limits. No correlation between SRF input and metal emission was observed.

  6. Evaluation of a zirconium additive for the mitigation of molten ash formation during combustion of residual fuel oil

    SciTech Connect

    1996-12-01

    Florida Power & Light Company (FP&L) currently fires a residual fuel oil (RFO) containing catalyst fines, which results in a troublesome black aluminosilicate liquid phase that forms on heat-transfer surfaces, remains molten, and flows to the bottom of the boiler. When the unit is shut down for a scheduled outage, this liquid phase freezes to a hard black glass that damages the contracting waterwalls of the boiler. Cleaning the boiler bottom and repairing damaged surfaces increase the boiler downtime, at a significant cost to FP&L. The Energy & Environmental Research Center (EERC) proposed to perform a series of tests for FP&L to evaluate the effectiveness of a zirconium additive to modify the mechanism that forms this liquid phase, resulting in the formation of a dry refractory phase that may be easily handled during cleanup of the boiler.

  7. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study

    NASA Astrophysics Data System (ADS)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  8. PLUVIUS: a generalized one-dimensional model of reactive pollutant behavior, including dry deposition, precipitation formation, and wet removal. Second edition

    SciTech Connect

    Easter, R.C.; Hales, J.M.

    1984-11-01

    This report is a second-edition user's manual for the PLUVIUS reactive-storm model. The PLUVIUS code simulates the formation of storm systems of a variety of types, and characterizes the behavior of air pollutants as they flow through, react within, and are scavenged by the storms. The computer code supplied with this report is known as PLUVIUS MOD 5.0, and is a substantial improvement over the MOD 3.1 version given in the original user's manual. Example applications of MOD 5.0 are given in the report to facilitate rapid application of the code for a variety of specific uses. 22 references, 7 figures, 48 tables.

  9. Novel Pathways of Nitroaromatic Metabolism: Hydroxylamine Formation, Reactivity and Potential for Ring Fission for Destruction of TNT-CU1214

    DTIC Science & Technology

    2005-08-15

    the anaerobic organism Clostridia acetobutylicum and the aerobic organism Pseudomonas pseudoalcaligenes strain JS45. The reactivity of partially...information exists (Alvarez, Kitts et al. 1995). Pseudomonas pseudoalcaligenes strains JS52 and JS45 grow aerobically on nitrobenzene using an initial...nitrobenzene nitroreductase from Pseudomonas pseudoalcaligenes can catalyze the transformation of TNT to 4- hydroxylamino-2,6-dinitrotoluene and then to 2,4

  10. Is sperm freezability related to the post-thaw lipid peroxidation and the formation of reactive oxygen species in boars?

    PubMed

    Gómez-Fernández, J; Gómez-Izquierdo, E; Tomás, C; Mocé, E; de Mercado, E

    2013-04-01

    The aim of the present study was to determine whether the levels of reactive oxygen species (ROS) substances production and the levels of lipid peroxidation of the sperm membrane were related to the quality that the ejaculates exhibited after cryopreservation in boars. Ejaculates from 42 healthy boars were used in this study and they were cryopreserved with the lactose-egg yolk extender (LEY). Several sperm quality parameters were assessed by flow cytometry in samples incubated for 30 and 150 min at 37 °C after thawing: the percentage of sperm with intact plasma membrane (SIPM), intracellular reactive oxygen substances production through mean of DCF fluorescence intensity of total sperm (mean-DCF) and the percentage of viable and non-viable sperm containing oxidized BODIPY (VSOB and NVSOB). In addition, the percentages of total motile (TMS) and progressively motile sperm (PMS) were assessed at the same incubation times with a computer-assisted sperm analysis system. The classification of the ejaculates into good or bad freezers was performed through hierarchical cluster analysis from SIPM and TMS at 150 min post-thawing. The ejaculates of those males classified as good freezers exhibited higher (p < 0.05) SPIM, TMS and PMS than the bad freezers, although both groups presented similar (p > 0.05) VSOB, NVSOB and mean-DCF. Therefore, these results show that lipid peroxidation and the amount of reactive oxygen substances in the sperm after cryopreservation are similar between boars classified as good or bad freezers.

  11. Berkeley Prize: Mapping the Fuel for Star Formation in Early Universe Galaxies

    NASA Astrophysics Data System (ADS)

    Tacconi, Linda

    2012-01-01

    Stars form from cold molecular interstellar gas, which is relatively rare in galaxies like the Milky Way, which form only a few new stars per year. Massive galaxies in the distant universe formed stars much more rapidly. Was star formation more efficient in the past, and/or were early galaxies richer in molecular gas? The answer was elusive when our instruments could probe molecules only in the most luminous and rare objects such as mergers and quasars. But a new survey of molecular gas in typical massive star-forming galaxies at redshifts from about 1.2 to 2.3 (corresponding to when the universe was 24% to 40% of its current age) reveals that distant star-forming galaxies were indeed molecular-gas rich and that the star-formation efficiency is not strongly dependent on cosmic epoch.

  12. Soot Formation and Destruction in High-Pressure Flames with Real Fuels

    DTIC Science & Technology

    2013-08-18

    Optical investigations on soot forming methane - oxygen flames,‟ Combust. Sci. Tech. 5, 263 (1972). D‟Anna, D. and Kent, J.H., „Aromatic formation...07/31/2013 8.00 Wei Jing, William L. Roberts, Tiegang Fang. Effects of Temperature and Oxygen on Spray and Combustion Characteristics of Diesel and...Temperature and Oxygen Concentration on Diesel Spray Combustion Using a Single-Nozzle Injector in a Constant Volume Combustion Chamber, Combustion

  13. Carbon monoxide formation in UO 2 kerneled HTR fuel particles containing oxygen getters

    NASA Astrophysics Data System (ADS)

    Proksch, E.; Strigl, A.; Nabielek, H.

    1986-06-01

    Mass spectrometric measurements of CO in irradiated UO 2 kerneled HTR fuel particles containing various oxygen getters are summarized and evaluated. Uranium carbide addition in the 3 to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, only somewhat ambiguous results have been obtained; most likely, ZrC results in CO reduction by a factor of about 40. Ce 2O 3 and La 2O 3 seem to be somewhat less effective than the three carbides; for Ce 2O 3, reduction factors between 3 and 15 have been found. However, these results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO 2 + Al 2O 3 has no influence on CO release at all.

  14. Droplet and slug formation in polymer electrolyte membrane fuel cell flow channels: The role of interfacial forces

    NASA Astrophysics Data System (ADS)

    Colosqui, Carlos E.; Cheah, May J.; Kevrekidis, Ioannis G.; Benziger, Jay B.

    A microfluidic device is employed to emulate water droplet emergence from a porous electrode and slug formation in the gas flow channel of a PEM fuel cell. Liquid water emerges from a 50 μm pore forming a droplet; the droplet grows to span the entire cross-section of a microchannel and transitions into a slug which detaches and is swept downstream. Droplet growth, slug formation, detachment, and motion are analyzed using high-speed video images and pressure-time traces. Slug volume is controlled primarily by channel geometry, interfacial forces, and gravity. As water slugs move downstream, they leave residual micro-droplets that act as nucleation sites for the next droplet-to-slug transition. Residual liquid in the form of micro-droplets results in a significant decrease in slug volume between the very first slug formed in an initially dry channel and the ultimate "steady-state" slug. A physics-based model is presented to predict slug volumes and pressure drops for slug detachment and motion.

  15. Influence of fuel on phase formation of ZnFe{sub 2}O{sub 4} prepared by self-propagated combustion route

    SciTech Connect

    Venkatesan, K.; Babu, D. Rajan

    2015-06-24

    Zinc iron oxide (ZnFe{sub 2}O{sub 4}) nanoparticles were prepared by self-propagated combustion route.The fuel plays a major role on the formation of structure and particle size. Here three different fuels like alanine, glycine and proline were used to synthesis the zinc iron oxide nanoparticle. Influence of combustion nature through the fuel, the phase formation, particle size, band gap and surface morphology has been modified. The prepared powder was characterized by powder X-ray diffraction method (PXRD), field-emission scanning electron microscopy (FE-SEM) and the composition of the material was analysed by X-ray energy dispersive spectroscopy (EDAX).The elemental mapping was confirmed the uniform distribution of Zn, Fe and O elements in the prepared material of ZnFe{sub 2}O{sub 4}.

  16. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    PubMed

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  17. Investigation of carbon-formation mechanisms and fuel-conversion rates in the adiabatic reformer. Annual report, March 19, 1980-March 19, 1981

    SciTech Connect

    Not Available

    1981-01-01

    Fuel cell power plants may be required to use coal derived liquid fuels or heavy petroleum distillates as fuels. Among the fuel processor candidates, the adiabatic reformer is at the most advanced state of development. The objective of the present program is to establish a reactor model for the adiabatic reformer which will predict process stream compositions and include carbon formation processes. Four subordinate tasks were proposed to achieve the objective. These are: 1) to determine on selected catalysts rate expressions for catalytic reactions occurring in the entrance section of the adiabatic reformer; 2) to determine with microbalance experiments critical conditions for carbon formation on selected catalysts; 3) to establish a reactor model to predict process stream compositions in the adiabatic reformer using data from Task 1 for catalytic reactions and data from the literature for homogeneous gas phase reactions; and 4) to establish a model to predict carbon formation by combination of the model for process stream composition from Task 3 and data for carbon formation from Task 2. Progress is reported. (WHK)

  18. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

    SciTech Connect

    Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu; Lin, Ying-Hsuan; Bhathela, Neil A.; Ortega, John; Worton, David; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Gold, Avram; Surratt, Jason D.

    2014-04-08

    Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.

  19. Thermal formation of hydroxynitriles, precursors of hydroxyacids in astrophysical ice analogs: Acetone ((CH3)2Cdbnd O) and hydrogen cyanide (HCN) reactivity

    NASA Astrophysics Data System (ADS)

    Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

    2015-11-01

    Reactivity in astrophysical environments is still poorly understood. In this contribution, we investigate the thermal reactivity of interstellar ice analogs containing acetone ((CH3)2CO), ammonia (NH3), hydrogen cyanide (HCN) and water (H2O) by means of infrared spectroscopy and mass spectrometry techniques, complemented by quantum chemical calculations. We show that no reaction occurs in H2O:HCN:(CH3)2CO ices. Nevertheless, HCN does indeed react with acetone once activated by NH3 into CN- to form 2-hydroxy-2-methylpropanenitrile (HOsbnd C(CH3)2sbnd CN), with a calculated activation energy associated with the rate determining step of about 51 kJ mol-1. This reaction inhibits the formation of 2-aminopropan-2-ol (HOsbnd C(CH3)2sbnd NH2) from acetone and NH3, even in the presence of water, which is the first step of the Strecker synthesis to form 2-aminoisobutyric acid (NH2C(CH3)2COOH). However, HOsbnd C(CH3)2sbnd CN formation could be part of an alternative chemical pathway leading to 2-hydroxy-2-methyl-propanoic acid (HOC(CH3)2COOH), which could explain the presence of hydroxy acids in some meteorites.

  20. Formation of diatomic molecular radicals in reactive nitrogen-carbon plasma generated by electron cyclotron resonance discharge and pulsed laser ablation

    SciTech Connect

    Liang, Peipei; Li, Yanli; You, Qinghu; Cai, Hua; Yang, Xu; Sun, Jian; Xu, Ning; Wu, Jiada

    2014-04-15

    The reactive nitrogen-carbon plasma generated by electron cyclotron resonance (ECR) microwave discharge of N{sub 2} gas and pulsed laser ablation of a graphite target was characterized spectroscopically by time-integrated and time-resolved optical emission spectroscopy with space resolution for a study of gas-phase reactions and molecular radical formation in the plasma. The plasma exhibits very high reactivity compared with the plasma generated solely by ECR discharge or by pulsed laser ablation and contains highly excited species originally present in the ambient gaseous environment and directly ablated from the target as well as formed as the products of gas-phase reactions occurring in the plasma. The space distribution and the time evolution of the plasma emission give an access to the gas-phase reactions for the formation of C{sub 2} and CN radicals, revealing that C{sub 2} radicals are formed mainly in the region near the target while CN radicals can be formed in a much larger region not only in the vicinity of the target, but especially in the region near a substrate far away from the target.

  1. Formation of diatomic molecular radicals in reactive nitrogen-carbon plasma generated by electron cyclotron resonance discharge and pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Liang, Peipei; Li, Yanli; You, Qinghu; Cai, Hua; Yang, Xu; Sun, Jian; Xu, Ning; Wu, Jiada

    2014-04-01

    The reactive nitrogen-carbon plasma generated by electron cyclotron resonance (ECR) microwave discharge of N2 gas and pulsed laser ablation of a graphite target was characterized spectroscopically by time-integrated and time-resolved optical emission spectroscopy with space resolution for a study of gas-phase reactions and molecular radical formation in the plasma. The plasma exhibits very high reactivity compared with the plasma generated solely by ECR discharge or by pulsed laser ablation and contains highly excited species originally present in the ambient gaseous environment and directly ablated from the target as well as formed as the products of gas-phase reactions occurring in the plasma. The space distribution and the time evolution of the plasma emission give an access to the gas-phase reactions for the formation of C2 and CN radicals, revealing that C2 radicals are formed mainly in the region near the target while CN radicals can be formed in a much larger region not only in the vicinity of the target, but especially in the region near a substrate far away from the target.

  2. Effect of biofilm formation on the performance of microbial fuel cell for the treatment of palm oil mill effluent.

    PubMed

    Baranitharan, E; Khan, Maksudur R; Prasad, D M R; Teo, Wee Fei Aaron; Tan, Geok Yuan Annie; Jose, Rajan

    2015-01-01

    Anode biofilm is a crucial component in microbial fuel cells (MFCs) for electrogenesis. Better knowledge about the biofilm development process on electrode surface is believed to improve MFC performance. In this study, double-chamber microbial fuel cell was operated with diluted POME (initial COD = 1,000 mg L(-1)) and polyacrylonitrile carbon felt was used as electrode. The maximum power density, COD removal efficiency and Coulombic efficiency were found as 22 mW m(-2), 70 and 24 %, respectively. FTIR and TGA analysis confirmed the formation of biofilm on the electrode surface during MFC operation. The impact of anode biofilm on anodic polarization resistance was investigated using electrochemical impedance spectroscopy (EIS) and microbial community changes during MFC operation using denaturing gradient gel electrophoresis (DGGE). The EIS-simulated results showed the reduction of charge transfer resistance (R ct) by 16.9 % after 14 days of operation of the cell, which confirms that the development of the microbial biofilm on the anode decreases the R ct and therefore improves power generation. DGGE analysis showed the variation in the biofilm composition during the biofilm growth until it forms an initial stable microbial community, thereafter the change in the diversity would be less. The power density showed was directly dependent on the biofilm development and increased significantly during the initial biofilm development period. Furthermore, DGGE patterns obtained from 7th and 14th day suggest the presence of less diversity and probable functional redundancy within the anodic communities possibly responsible for the stable MFC performance in changing environmental conditions.

  3. Where does the gas fueling star formation in brightest cluster galaxies originate?

    NASA Astrophysics Data System (ADS)

    Molendi, S.; Tozzi, P.; Gaspari, M.; De Grandi, S.; Gastaldello, F.; Ghizzardi, S.; Rossetti, M.

    2016-11-01

    Aims: We investigate the relationship between X-ray cooling and star formation in brightest cluster galaxies (BCGs). Methods: We present an X-ray spectral analysis of the inner regions, 10-40 kpc, of six nearby cool core clusters (z < 0.35) observed with Chandra ACIS. This sample is selected on the basis of the high star formation rate (SFR) observed in the BCGs. We restrict our search for cooling gas to regions that are roughly cospatial with the starburst. We fit single- and multi-temperature mkcflow models to constrain the amount of isobarically cooling intracluster medium. Results: We find that in all clusters, below a threshold temperature ranging between 0.9 and 3 keV, only upper limits can be obtained. In four out of six objects, the upper limits are significantly below the SFR and in two, namely A1835 and A1068, they are less than a tenth of the SFR. Conclusions: Our results suggests that a number of mechanisms conspire to hide the cooling signature in our spectra. In a few systems the lack of a cooling signature may be attributed to a relatively long delay time between the X-ray cooling and the star burst. However, for A1835 and A1068, where the X-ray cooling time is shorter than the timescale of the starburst, a possible explanation is that the region where gas cools out of the X-ray phase extends to very large radii, likely beyond the core of these systems.

  4. Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge.

    PubMed

    Åmand, Lars-Erik; Kassman, Håkan

    2013-08-01

    Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW(th) circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.

  5. Deoxyelephantopin impedes mammary adenocarcinoma cell motility by inhibiting calpain-mediated adhesion dynamics and inducing reactive oxygen species and aggresome formation.

    PubMed

    Lee, Wai-Leng; Shyur, Lie-Fen

    2012-04-15

    We previously showed that deoxyelephantopin (DET), a plant sesquiterpene lactone, exhibits more profound suppression than paclitaxel (PTX) of lung metastasis of mammary adenocarcinoma TS/A cells in mice. Proteomics studies suggest that DET affects actin cytoskeletal protein networks and downregulates calpain-mediated proteolysis of several actin-associated proteins, whereas PTX mainly interferes with microtubule proteins. Here, DET was observed to significantly deregulate adhesion formation in TS/A cells, probably through inhibition of m-calpain activity. Epithelial growth factor (EGF)-mediated activation of Rho GTPase Rac1 and formation of lamellipodia in TS/A cells were remarkably suppressed by DET treatment. Further, DET impaired vesicular trafficking of EGF and induced protein carbonylation and formation of centrosomal aggregates in TS/A cells. DET-induced reactive oxygen species were observed to be the upstream stimulus for the formation of centrosomal ubiquitinated protein aggregates that might subsequently restrict cancer cell motility. PTX, however, caused dramatic morphological changes, interfered with microtubule networking, and moderately inhibited calpain-mediated cytoskeletal and focal adhesion protein cleavage in TS/A cells. This study provides novel mechanistic insights into the pharmacological action of DET against metastatic mammary cell migration and suggests that modulation of oxidative stress might be a potential strategy for treatment of metastatic breast cancer.

  6. Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

    SciTech Connect

    Åmand, Lars-Erik; Kassman, Håkan

    2013-08-15

    Highlights: • Two strategies to reduce PCDD/F formation when co-firing solid recovered fuel (SRF) and biomass. • They were co-combustion with municipal sewage sludge (MSS) and addition of ammonium sulphate. • PCDD/Fs were significantly reduced for a biomass rich in chlorine when adding ammonium sulphate. • MSS had a suppressing effect on PCDD/F formation during co-combustion with SRF. • A link is presented between gaseous alkali chlorides, chlorine in deposits and PCDD/F formation. - Abstract: Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW{sub th} circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS

  7. Prooxidant action of furanone compounds: implication of reactive oxygen species in the metal-dependent strand breaks and the formation of 8-hydroxy-2'-deoxyguanosine in DNA.

    PubMed

    Murakami, K; Haneda, M; Makino, T; Yoshino, M

    2007-07-01

    Prooxidant properties of furanone compounds including 2,5-furanone (furaneol, 4-hydroxy-2,5-dimethyl-furan-3-one), 4,5-furanone (4,5-dimethyl-3-hydroxy-2(5H)-furanone) (sotolone) and cyclotene (2-hydroxy-3-methyl-2-cyclopenten-1-one) were analyzed in relation to the metal-reducing activity. Only 2.5-furanone known as a "strawberry or pineapple furanone" inactivated aconitase the most sensitive enzyme to active oxygen in the presence of ferrous sulfate, suggesting the furaneol/iron-mediated generation of reactive oxygen species. 2,5-Furanone caused strand scission of pBR322 DNA in the presence of copper. Treatment of calf thymus DNA with 2,5-furanone plus copper produced 8-hydroxy-2'-deoxyguanosine in DNA. 2,5-Furanone showed a potent copper-reducing activity, and thus, DNA strand breaks and the formation of 8-hydroxy-2'-deoxyguanosine by 2,5-furanone can be initiated by the production of superoxide radical through the reduction of cupric ion to cuprous ion, resulting in the conversion to hydrogen peroxide and hydroxyl radical. However, an isomer and analog of 2,5-furanone, 4,5-furanone and cyclotene, respectively, did not show an inactivation of aconitase, DNA injuries including strand breakage and the formation of 8-hydroxy-2'-deoxyguanosine, and copper-reducing activity. Cytotoxic effect of 2,5-furanone with hydroxyketone structure can be explained by its prooxidant properties: furaneol/transition metal complex generates reactive oxygen species causing the inactivation of aconitase and the formation of DNA base damage by hydroxyl radical.

  8. Effect of hydrocarbon fuel type on fuel

    NASA Technical Reports Server (NTRS)

    Wong, E. L.; Bittker, D. A.

    1982-01-01

    A modified jet fuel thermal oxidation tester (JFTOT) procedure was used to evaluate deposit and sediment formation for four pure hydrocarbon fuels over the temperature range 150 to 450 C in 316-stainless-steel heater tubes. Fuel types were a normal alkane, an alkene, a naphthene, and an aromatic. Each fuel exhibited certain distinctive deposit and sediment formation characteristics. The effect of aluminum and 316-stainless-steel heater tube surfaces on deposit formation for the fuel n-decane over the same temperature range was investigated. Results showed that an aluminum surface had lower deposit formation rates at all temperatures investigated. By using a modified JFTOT procedure the thermal stability of four pure hydrocarbon fuels and two practical fuels (Jet A and home heating oil no. 2) was rated on the basis of their breakpoint temperatures. Results indicate that this method could be used to rate thermal stability for a series of fuels.

  9. Phosphorylcholine functionalized dendrimers for the formation of highly stable and reactive gold nanoparticles and their glucose conjugation for biosensing

    NASA Astrophysics Data System (ADS)

    Jia, Lan; Lv, Li-Ping; Xu, Jian-Ping; Ji, Jian

    2011-09-01

    Phosphorylcholine (PC)-functionalized poly(amido amine) (PAMAM) dendrimers were prepared and used as both reducing and stabilizing agents for synthesis of highly stable and reactive gold nanoparticles (Au NPs). Biomimetic PC-functionalized PAMAM dendrimers-stabilized gold nanoparticles (Au DSNPs) were formed by simply mixing the PC modified amine-terminated fifth-generation PAMAM dendrimers (G5-PC) with AuCl4 - ions by controlling the pH, no additional reducing agents or other stabilizers were needed. The obtained Au DSNPs were shown to be spherical, with particle diameters ranging from 5 to 12 nm, the sizes and growth kinetics of Au DSNPs could be tuned by changing the pH and the initial molar ratio of dendrimers to gold as indicated by transmission electron microscopy (TEM) and UV-Vis data. The prepared Au DSNPs showed excellent stability including: (1) stable at wide pH (7-13) values; (2) stable at high salt concentrations up to 2 M NaCl; (3) non-specific protein adsorption resistance. More importantly, surface functionalization could be performed by introducing desired functional groups onto the remained reactive amine groups. This was exemplified by the glucose conjugation. The glucose conjugated Au DSNPs showed bio-specific interaction with Concanavalin A (Con A), which induced aggregation of the Au NPs. Colorimetric detection of Con A based on the plasmon resonance of the glucose conjugated Au DSNPs was realized. A limit of detection (LOD) for Con A was 0.6 μM, based on a signal-to-noise ratio (S/N) of 3. These findings demonstrated that the PC modified Au DSNPs could potentially serve as a versatile nano-platform for the biomedical applications.

  10. Determination of the boundary of carbon formation for dry reforming of methane in a solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Assabumrungrat, S.; Laosiripojana, N.; Piroonlerkgul, P.

    The boundary of carbon formation for the dry reforming of methane in direct internal reforming solid oxide fuel cells (DIR-SOFCs) with different types of electrolyte (i.e., an oxygen ion-conducting electrolyte (SOFC-O 2-) and a proton-conducting electrolyte (SOFC-H +)) was determined by employing detailed thermodynamic analysis. It was found that the required CO 2/CH 4 ratio decreased with increasing temperature. The type of electrolyte influenced the boundary of carbon formation because it determined the location of water formed by the electrochemical reaction. The extent of the electrochemical reaction also played an important role in the boundary of carbon formation. For SOFC-O 2-, the required CO 2/CH 4 ratio decreased with the increasing extent of the electrochemical reaction due to the presence of electrochemical water in the anode chamber. Although for SOFC-H + the required CO 2/CH 4 ratio increased with the increasing extent of the electrochemical reaction at high operating temperature (T > 1000 K) following the trend previously reported for the case of steam reforming of methane with addition of water as a carbon suppresser, an unusual opposite trend was observed at lower operating temperature. The study also considered the use of water or air as an alternative carbon suppresser for the system. The required H 2O/CH 4 ratio and air/CH 4 ratio were determined for various inlet CO 2/CH 4 ratios. Even air is a less attractive choice compared to water due to the higher required air/CH 4 ratio than the H 2O/CH 4 ratio; however, the integration of exothermic oxidation and the endothermic reforming reactions may make the use of air attractive. Water was found to be more effective than carbon dioxide in suppressing the carbon formation at low temperatures but their effect was comparable at high temperatures. Although the results from the study were based on calculations of the SOFCs with different electrolytes, they are also useful for selecting suitable feed

  11. Fuel effects on soot formation in turbojet engines. Progress report 15 Sep 83-14 Mar 84

    SciTech Connect

    Olson, D.B.; Gill, R.J.

    1984-05-04

    The sooting tendencies of sixteen Navy jet fuels and eight fuel blending components have been studied in laboratory flames to compare with results obtained in other programs using these fuels in turbojet engines and combustors. The average molecular weight, density, ASTM smoke point, and diffusion flame and premixed flame threshold sooting index of each fuel have been measured. An apparatus has been assembled to measure premixed flame soot yields using a multi-wavelength laser extinction technique. Experiments have been performed on a six-component test fuel blended using pure hydrocarbon components. The diffusion flame soot threshold of this fuel can be predicted using the pure component values but the predicted premixed flame soot threshold is larger than measured. Experiments are planned to measure soot yields of the jet fuels and to correlate the laboratory measurements with engine test results.

  12. Asbestos fibers and interleukin-1 upregulate the formation of reactive nitrogen species in rat pleural mesothelial cells.

    PubMed

    Choe, N; Tanaka, S; Kagan, E

    1998-08-01

    Nitric oxide radical (.NO) and peroxynitrite anion (ONOO-) have been implicated in lung inflammation and may be important in pleural injury. The present study was undertaken to determine the effects of asbestos exposure and cytokine stimulation on .NO and ONOO- production by rat pleural mesothelial cells. Accordingly, rat parietal pleural mesothelial cells were cultured for 2 to 72 h with or without 50 ng/ml of recombinant interleukin-1beta (IL-1beta) in the presence (1.05 to 8.4 microg/cm2) or absence of crocidolite or chrysotile asbestos fibers. The effects of asbestos were compared with those of carbonyl iron, a nonfibrogenic particulate. Mesothelial cell messenger RNA (mRNA) expression of the inducible form of .NO synthase (iNOS), assessed with the reverse transcription-polymerase chain reaction (RT-PCR), increased progressively from 2 to 12 h in IL-1beta-containing cultures. Nitrite (NO2-), the stable oxidation product of .NO in mesothelial cell conditioned medium, was assayed through the Griess reaction. Both types of asbestos fibers (chrysotile > crocidolite) upregulated the formation of NO2- in mesothelial cells costimulated with IL-1beta in a concentration-dependent and time-dependent fashion. In contrast, carbonyl iron did not upregulate NO2- formation in IL-1beta-stimulated cells. Both types of asbestos fibers also induced iNOS protein expression and the formation of nitrotyrosine in mesothelial cells and greatly induced the formation of nitrate (NO3-), a surrogate marker of ONOO- formation, in IL-1beta-stimulated cells. However, the effects of chrysotile were notably greater than those of crocidolite. These findings may have significance for the induction of pleural injury by asbestos fibers.

  13. Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion.

    PubMed

    Chen, Juan; Jiao, Facun; Zhang, Lian; Yao, Hong; Ninomiya, Yoshihiko

    2013-10-15

    The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca(2+) with high reduction potential favored the oxidation of Cr(III), same for K(+). The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash.

  14. Jet fuel instability mechanisms

    NASA Technical Reports Server (NTRS)

    Daniel, S. R.

    1985-01-01

    The mechanisms of the formation of fuel-insoluble deposits were studied in several real fuels and in a model fuel consisting of tetralin in dodecane solution. The influence of addition to the fuels of small concentrations of various compounds on the quantities of deposits formed and on the formation and disappearance of oxygenated species in solution was assessed. The effect of temperature on deposit formation was also investigated over the range of 308-453 K.

  15. Reactive Uptake of Ammonia and Formation of Organic Nitrogen Species for Non-Liquid/Liquid Secondary Organic Material

    NASA Astrophysics Data System (ADS)

    Martin, S. T.; Li, Y.; Liu, P.

    2015-12-01

    Formation of ammonium and organic nitrogen (ON) species was studied for secondary organic material (SOM) of variable viscosity, ranging from non-liquid to liquid physical states. The SOM was produced as particles of 50 to 150 nm in diameter in aerosol form from six precursors, including three terpenoid and three aromatic species. The viscosity of the hygroscopic SOM was adjusted by exposure to relative humidity (RH) from <5% to >90% RH in steps of 10% at 293 ± 2 K. The aerosol was subsequently exposed to 5 ppm NH3 for mean reaction times of 30, 370, or 5230 s. Ammonium and ON were characterized by high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). The ammonium-to-organic ratio of mass concentrations (MNH4/MOrg) in the particles increased monotonically from <5% RH to a limiting value at a threshold RH, implicating a switchover in the reaction kinetics from a system limited by diffusivity within the SOM for low RH to one limited by other factors, such as saturated uptake, at higher RH. Formation of ON was observed for aromatic-derived SOMs, but not significant for terpenoid-derived SOMs. For aromatic-derived SOMs, the ON-to-organic ratio of mass concentrations (MON/MOrg) was negligible for RH <20%, increased monotonically from 20% to 60% RH, and stayed constant for RH >60%. The threshold RH for the switchover from kinetically controlled regime to a non-kinetically-controlled one was thus different between formation of ammonium and ON. This difference suggests that water may play a role in the slow reactions of ON formation as a reactant or a catalyst, in addition to affecting the reactant diffusion as in the fast reaction of ammonium formation. The implication is that formation of ammonium salts and organic nitrogen species by certain SOMs should be treated separately in chemical transport models to reflect the different roles of water that may affect the phase state of the SOMs or may act as a reactant or a catalyst.

  16. Reactive oxygen species at the oxide/water interface: Formation mechanisms and implications for prebiotic chemistry and the origin of life

    NASA Astrophysics Data System (ADS)

    Xu, Jie; Sahai, Nita; Eggleston, Carrick M.; Schoonen, Martin A. A.

    2013-02-01

    The goal of our study is to identify free radical formation pathways on mineral surfaces. Organic molecules on early Earth might have been modified or decomposed by such pathways, thus affecting the total organic inventory for prebiotic synthesis reactions. Specifically, we evaluated several common oxide minerals under a range of environmental conditions and combinations of conditions (pH, O2 level, UV-wavelength, and particle loading), for formation of highly reactive oxygen species (ROS) at the oxide surfaces by quantifying the generated [OHrad ] and [H2O2]. We identified anatase/rutile (β-TiO2/α-TiO2) and hematite (α-Fe2O3) as active in ROS production and, importantly, found different dominant pathways for ROS formation on anatase/rutile versus hematite. Hydroxyl radicals (OHrad ) in anatase and rutile suspensions were generated mainly through the oxidation of OH- by photo-generated holes and H2O2 was generated through the combination of an OHrad radical with an OH- and a hole. This pathway for the TiO2 phases did not require the presence of O2, and was not shut down under anaerobic conditions. In contrast, formation of H2O2 and OHrad in hematite suspensions involved reduction of O2 by electrons, which was inhibited under anaerobic conditions. The surface ROS as well as free radicals formed by reactions with other gases on early Earth atmosphere were capable of destroying molecules such as lipids and pre-RNA or RNA essential to assembly of protocells and survival of the earliest cells. At the same time, surface associated ROS and other free radicals may also have promoted aminoamide formation. Thus, the surface ROS would have affected prebiotic organic compound inventory and protocell/early life evolution.

  17. Phenol-Soluble Modulin α Peptide Toxins from Aggressive Staphylococcus aureus Induce Rapid Formation of Neutrophil Extracellular Traps through a Reactive Oxygen Species-Independent Pathway

    PubMed Central

    Björnsdottir, Halla; Dahlstrand Rudin, Agnes; Klose, Felix P.; Elmwall, Jonas; Welin, Amanda; Stylianou, Marios; Christenson, Karin; Urban, Constantin F.; Forsman, Huamei; Dahlgren, Claes; Karlsson, Anna; Bylund, Johan

    2017-01-01

    Neutrophils have the ability to capture and kill microbes extracellularly through the formation of neutrophil extracellular traps (NETs). These are DNA and protein structures that neutrophils release extracellularly and are believed to function as a defense mechanism against microbes. The classic NET formation process, triggered by, e.g., bacteria, fungi, or by direct stimulation of protein kinase C through phorbol myristate acetate, is an active process that takes several hours and relies on the production of reactive oxygen species (ROS) that are further modified by myeloperoxidase (MPO). We show here that NET-like structures can also be formed by neutrophils after interaction with phenol-soluble modulin α (PSMα) that are cytotoxic membrane-disturbing peptides, secreted from community-acquired methicillin-resistant Staphylococcus aureus (CA-MRSA). The PSMα-induced NETs contained the typical protein markers and were able to capture microbes. The PSMα-induced NET structures were disintegrated upon prolonged exposure to DNase-positive S. aureus but not on exposure to DNase-negative Candida albicans. Opposed to classic NETosis, PSMα-triggered NET formation occurred very rapidly, independently of ROS or MPO, and was also manifest at 4°C. These data indicate that rapid NETs release may result from cytotoxic membrane disturbance by PSMα peptides, a process that may be of importance for CA-MRSA virulence. PMID:28337204

  18. Evaluation of the probe dihydrocalcein acetoxymethylester as an indicator of reactive oxygen species formation and comparison with oxidative DNA base modification determined by modified alkaline elution technique.

    PubMed

    Rohnstock, A; Lehmann, L

    2007-12-01

    Reactive oxygen species (ROS) play a predominant role in various diseases and the development of fast and easy methods for the quantification of intracellular ROS represents an important goal. Therefore, the aim of the present study was the evaluation of the fluorogenic probe dihydrocalcein acetoxymethylester (AM) for the detection of intracellular ROS. A flow cytometric method was developed using MCF-7 cells and the kinetics of ester hydrolysis and the cellular distribution and stability of calcein were characterized using calcein AM. Then, MCF-7 cells were challenged with model agents for the generation of singlet oxygen (illumination with visible light), peroxyl and hydroxyl radicals (tert-butylhydroperoxide, tBHP), superoxide anion radicals (potassium dioxide), and the intracellular formation of superoxide anion radicals by redox cycling (menadione) and the formation of calcein was compared with the induction of oxidative DNA base modifications assessed by modified alkaline elution technique. Every model agent significantly induced formamidopyrimidine-DNA glycosylase-sensitive sites (i.e. oxidative DNA base modifications) and most also induced DNA strand breaks. In contrast, exclusively tBHP and illumination with visible light induced the intracellular formation of calcein. In conclusion, though intracellular oxidation of dihydrocalcein represents a fast screening method, it detects a limited spectrum of ROS.

  19. Phenol-Soluble Modulin α Peptide Toxins from Aggressive Staphylococcus aureus Induce Rapid Formation of Neutrophil Extracellular Traps through a Reactive Oxygen Species-Independent Pathway.

    PubMed

    Björnsdottir, Halla; Dahlstrand Rudin, Agnes; Klose, Felix P; Elmwall, Jonas; Welin, Amanda; Stylianou, Marios; Christenson, Karin; Urban, Constantin F; Forsman, Huamei; Dahlgren, Claes; Karlsson, Anna; Bylund, Johan

    2017-01-01

    Neutrophils have the ability to capture and kill microbes extracellularly through the formation of neutrophil extracellular traps (NETs). These are DNA and protein structures that neutrophils release extracellularly and are believed to function as a defense mechanism against microbes. The classic NET formation process, triggered by, e.g., bacteria, fungi, or by direct stimulation of protein kinase C through phorbol myristate acetate, is an active process that takes several hours and relies on the production of reactive oxygen species (ROS) that are further modified by myeloperoxidase (MPO). We show here that NET-like structures can also be formed by neutrophils after interaction with phenol-soluble modulin α (PSMα) that are cytotoxic membrane-disturbing peptides, secreted from community-acquired methicillin-resistant Staphylococcus aureus (CA-MRSA). The PSMα-induced NETs contained the typical protein markers and were able to capture microbes. The PSMα-induced NET structures were disintegrated upon prolonged exposure to DNase-positive S. aureus but not on exposure to DNase-negative Candida albicans. Opposed to classic NETosis, PSMα-triggered NET formation occurred very rapidly, independently of ROS or MPO, and was also manifest at 4°C. These data indicate that rapid NETs release may result from cytotoxic membrane disturbance by PSMα peptides, a process that may be of importance for CA-MRSA virulence.

  20. Characteristics of liquid stannum anode fuel cell operated in battery mode and CO/H2/carbon fuel mode

    NASA Astrophysics Data System (ADS)

    Wang, Hongjian; Shi, Yixiang; Cai, Ningsheng

    2014-01-01

    A liquid Stannum (Sn) anode fuel cell is fabricated by using smooth single crystal Yttria Stabilized Zirconia (YSZ) electrolyte and porous Pt cathode. The cell performance in the battery mode is tested to identify the intrinsic reaction kinetics of the Sn electrochemical oxidation reaction. The cell performance characteristics in the gas fuel mode and carbon fuel mode are experimentally measured to identify limiting steps in different operating modes. The results show that in the battery mode, the SnO2 film formation blocks the transportation path of the liquid Sn and oxygen ions to the reactive interface. In the gas fuel modes, the cell performance operating in the H2 fuel mode is much higher than that in the CO fuel mode which is ascribing to the effective reaction of the formed SnO2 at the reactive interface between electrolyte and anode. In the carbon fuel mode, the carbon black fuel can directly or indirectly reduce part of the SnO2 at the interface between anode and electrolyte. It apparently indicates that the performance improvements of liquid Sn anode direct carbon fuel cell rely on minimizing the effects of formed SnO2 layer and accelerating species transportation processes within the liquid Sn electrode.

  1. Switching from adduct formation to electron transfer in a light-oxygen-voltage domain containing the reactive cysteine.

    PubMed

    Magerl, Kathrin; Stambolic, Ivan; Dick, Bernhard

    2017-03-08

    LOV (light-, oxygen- or voltage-sensitive) domains act as photosensory units of many prokaryotic and eukaryotic proteins. Upon blue light excitation they undergo a photocycle via the excited triplet state of their flavin chromophore yielding the flavin-cysteinyl adduct. Adduct formation is highly conserved among all LOV domains and constitutes the primary step of LOV domain signaling. But recently, it has been shown that signal propagation can also be triggered by flavin photoreduction to the neutral semiquinone offering new prospects for protein engineering. This, however, requires mutation of the photo-active Cys. Here, we report on LOV1 mutants of C. reinhardtii phototropin in which adduct formation is suppressed although the photo-active Cys is present. Introduction of a Tyr into the LOV core induces a proton coupled electron transfer towards the flavin chromophore. Flavin radical species are formed via either the excited flavin singlet or triplet state depending on the geometry of donor and acceptor. This photoreductive pathway resembles the photoreaction observed in other blue light photoreceptors, e.g. blue-light sensors using flavin adenine dinucleotide (BLUF) domains or cryptochromes. The ability to tune the photoreactivity of the flavin chromophore inside the LOV core has implications for the mechanism of adduct formation in the wild type and may be of use for protein engineering.

  2. Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation.

    PubMed

    Elliott, Paul I P; Haak, Susanne; Meijer, Anthony J H M; Sunley, Glenn J; Haynes, Anthony

    2013-12-21

    The reactions of water with a number of iridium(III) complexes relevant to the mechanism for catalytic methanol carbonylation are reported. The iridium acetyl, [Ir(CO)2I3(COMe)](-), reacts with water under mild conditions to release CO2 and CH4, rather than the expected acetic acid. Isotopic labeling and kinetic experiments are consistent with a mechanism involving nucleophilic attack by water on a terminal CO ligand of [Ir(CO)2I3(COMe)](-) to give an (undetected) hydroxycarbonyl species. Subsequent decarboxylation and elimination of methane gives [Ir(CO)2I2](-). Similar reactions with water are observed for [Ir(CO)2I3Me](-), [Ir(CO)2(NCMe)I2(COMe)] and [Ir(CO)3I2Me] with the neutral complexes exhibiting markedly higher rates. The results demonstrate that CO2 formation during methanol carbonylation is not restricted to the conventional water gas shift mechanism mediated by [Ir(CO)2I4](-) or [Ir(CO)3I3], but can arise directly from key organo-iridium(III) intermediates in the carbonylation cycle. An alternative pathway for methane formation not involving the intermediacy of H2 is also suggested. A mechanism is proposed for the conversion MeOH + CO → CO2 + CH4, which may account for the similar rates of formation of the two gaseous by-products during iridium-catalysed methanol carbonylation.

  3. UVA Photoirradiation of Nitro-Polycyclic Aromatic Hydrocarbons—Induction of Reactive Oxygen Species and Formation of Lipid Peroxides †

    PubMed Central

    Xia, Qingsu; Yin, Jun J.; Zhao, Yuewei; Wu, Yuh-Sen; Wang, Yu-Qui; Ma, Liang; Chen, Shoujun; Sun, Xin; Fu, Peter P.; Yu, Hongtao

    2013-01-01

    Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) are a class of genotoxic environmental contaminants. We have long been interested in determining the mechanisms by which nitro-PAHs induce genotoxicity. Although the metabolic activation of nitro-PAHs leading to toxicological activities has been well studied, the photo-induced activation of nitro-PAHs has seldom been reported. In this paper, we report photo-induced lipid peroxidation by 19 nitro-PAHs. The results indicated that all but two of the nitro-PAHs can induce lipid peroxidation. Mechanistic studies suggest that lipid peroxidation by nitro-PAHs is mediated by free radicals generated in the reaction. There was no structural correlation between the nitro-PAHs and their ability to induce lipid peroxidation upon UVA irradiation, or between the HOMO-LUMO gap and the ability to cause lipid peroxidation. Most of the nitro-PAHs are less potent in terms of causing lipid peroxidation than their parent PAHs. The lack of correlation is attributed to the complex photophysics and photochemistry of the nitro-PAHs and the yield of reactive oxygen species (ROS) and other factors. PMID:23493032

  4. How covalent heme to protein bonds influence the formation and reactivity of redox intermediates of a bacterial peroxidase.

    PubMed

    Auer, Markus; Nicolussi, Andrea; Schütz, Georg; Furtmüller, Paul G; Obinger, Christian

    2014-11-07

    The most striking feature of mammalian peroxidases, including myeloperoxidase and lactoperoxidase (LPO) is the existence of covalent bonds between the prosthetic group and the protein, which has a strong impact on their (electronic) structure and biophysical and chemical properties. Recently, a novel bacterial heme peroxidase with high structural and functional similarities to LPO was described. Being released from Escherichia coli, it contains mainly heme b, which can be autocatalytically modified and covalently bound to the protein by incubation with hydrogen peroxide. In the present study, we investigated the reactivity of these two forms in their ferric, compound I and compound II state in a multi-mixing stopped-flow study. Upon heme modification, the reactions between the ferric proteins with cyanide or H2O2 were accelerated. Moreover, apparent bimolecular rate constants of the reaction of compound I with iodide, thiocyanate, bromide, and tyrosine increased significantly and became similar to LPO. Kinetic data are discussed and compared with known structure-function relationships of the mammalian peroxidases LPO and myeloperoxidase.

  5. Formation of hydrogenated amorphous carbon films by reactive high power impulse magnetron sputtering containing C2H2 gas

    NASA Astrophysics Data System (ADS)

    Kimura, Takashi; Kamata, Hikaru

    2015-09-01

    Diamond-like carbon (DLC) films have attracted interest for material industries, because they have unique properties. Hydrogenated amorphous carbon films are prepared by reactive high power impulse magnetron sputtering (HiPIMS) containing C2H2 gas and the properties of the films produced in Ar/C2H2 and Ne/C2H2 HiPIMS are compared. Production of hydrocarbon radicals and their ions strongly depends on both electron temperature and electron density in HiPIMS. Therefore, the influence of the difference in buffer gas (Ar and Ne) on the film properties is also valuable to investigate. The film preparation is performed at an average power of 60 W and a repetition frequency of 110 Hz. Total pressure ranges between 0.3 and 2 Pa. The maximum of instantaneous power is about 20-25 kW, and the magnitude of the current is 35 A. A negative pulse voltage is applied to the substrates for about 15 μs after the target voltage changed from about -500 V to 0 V. Hardness of the films prepared by Ar/C2H2 HiPIMS monotonically decreases with increasing the total pressure, whereas that of the films prepared by Ne/C2H2 HiPIMS does not strongly depend on the total pressure. This work is partially supported by JSPS KAKENHI Grant Number 26420230.

  6. Characterizing the chemical evolution of air masses via multi-platform measurements of volatile organic compounds (VOCs) during CalNEX: Composition, OH reactivity, and potential SOA formation

    NASA Astrophysics Data System (ADS)

    Gilman, J. B.; Kuster, W. C.; Bon, D.; Warneke, C.; Lerner, B. M.; Williams, E. J.; Holloway, J. S.; Pollack, I. B.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Herndon, S. C.; Zahniser, M. S.; Vlasenko, A. L.; Li, S.; Alvarez, S. L.; Rappenglueck, B.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; De Gouw, J. A.

    2011-12-01

    Volatile organic compounds (VOCs) are critical components in the photochemical production of ozone (O3) and secondary organic aerosol (SOA). During the CalNex 2010 field campaign, an extensive set of VOCs were measured at the Pasadena ground site, and aboard the NOAA WP-3D aircraft and the WHOI Research Vessel Atlantis. The measurements from each platform provide a unique perspective into the emissions, transport, and atmospheric processing of VOCs within the South Coast Air Basin (SoCAB). The observed enhancement ratios of the hydrocarbons measured on all three platforms are in good agreement and are generally well correlated with carbon monoxide (CO), indicating the prevalence of on-road VOC emission sources throughout the SoCAB. Offshore measurements aboard the ship and aircraft are used to characterize the air mass composition as a function of the land/sea-breeze effect. VOC ratios and other trace gases are used to identify air masses containing relatively fresh emissions that were often associated with offshore flow and re-circulated continental air associated with onshore flow conditions. With the prevailing southwesterly airflow pattern in the LAB throughout the daytime, the Pasadena ground site effectively functions as a receptor site and is used to characterize primary VOC emissions from downtown Los Angeles and to identify the corresponding secondary oxidation products. The chemical evolution of air masses as a function of the time of day is investigated in order to determine the relative impacts of primary emissions vs. secondary VOC products on OH reactivity and potential SOA formation. The reactivity of VOCs with the hydroxyl radical (OH) at the Pasadena site was dominated by the light hydrocarbons, isoprene, and oxygenated VOCs including aldehydes (secondary products) and alcohols (primary anthropogenic emissions). Toluene and benzaldehyde, both of which are associated with primary anthropogenic emissions, are the predominant VOC precursors to the

  7. Light-independent reactive oxygen species (ROS) formation through electron transfer from carboxylated single-walled carbon nanotubes in water.

    PubMed

    Hsieh, Hsin-Se; Wu, Renren; Jafvert, Chad T

    2014-10-07

    Promising developments in application of carbon nanotubes (CNTs) have raised concern regarding potential biological and environmental effects upon their inevitable release to the environment. Although some CNTs have been reported to generate reactive oxygen species (ROS) under light, limited information exists on ROS generation by these materials in the dark. In this study, generation of ROS was examined, initiated by electron transfer from biological electron donors through carboxylated single-walled carbon nanotubes (C-SWCNT) to molecular oxygen in water in the dark. In the presence of C-SWCNT, the oxidation of NADH (β-nicotinamide adenine dinucleotide, reduced form) and DTTre (DL-dithiothreitol, reduced form) was confirmed by light absorbance shifts (340 nm to 260 nm during oxidation of NADH to NAD(+), and increased light absorbance at 280 nm during oxidation of DTTre). Production of superoxide anion (O2(•-)) was detected by its selective reaction with a tetrazolium salt (NBT(2+)), forming a formazan product that is visible at 530 nm. A modified acid-quenched N,N-diethyl-p-phenylenediamine (DPD) assay was used to measure the accumulation of H2O2 in C-SWCNT suspensions containing O2 and NADH. In the same suspensions (i.e., containing C-SWCNT, NADH, and O2), pBR322 DNA plasmid was cleaved, although •OH was not detected when using •OH scavenging molecular probes. These results indicate that the oxidation of electron donors by C-SWCNT can be a light-independent source of ROS in water, and that electron shuttling through CNTs to molecular oxygen may be a potential mechanism for DNA damage by this specific CNT and potentially other carbon-based nanomaterials.

  8. Formation, characterization, and dynamics of onion-like carbon structures for electrical energy storage from nanodiamonds using reactive force fields

    SciTech Connect

    Ganesh, P.; Kent, P. R. C.; Mochalin, V.

    2011-10-01

    We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbonnanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core of the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbonnanostructure appears, with a shell-shell spacing of about ~3.4 Å for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large (~29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.

  9. Formation, characterization and dynamics of onion like carbon structures from nanodiamonds using reactive force-fields for electrical energy storage

    SciTech Connect

    Kent, Paul R

    2011-01-01

    We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core of the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.

  10. Studies of the formation, chemical reactivity, and properties of small clusters: Application to an understanding of aerosol formation and heterogeneous chemistry

    SciTech Connect

    Castleman, A.W. Jr.

    1990-01-01

    The small cluster program involves (1) studies of reactions related to formation and growth of heteromolecular clusters and their thermochemical properties, (2) studies of photoinitiated processes in clusters, (3) investigations related to heterogeneous reactions including the influence of reaction centers on the interconversion, and (4) theoretical calculations of properties, dynamics, and structure. A major thrust of the work during the past year has been devoted to a study of the role of ionization and the presence of ions on reactions and energetics. During the past few months, particular attention has been paid to systems having varying proton affinities. From the data, we can determine the influence of these values on the nature of the reactions and ascertain the ultimate chemical nature of the ionization center formed as a result of the reactions. 83 refs., 12 figs., 2 tabs.

  11. Redox Reactivity of Cerium Oxide Nanoparticles Induces the Formation of Disulfide Bridges in Thiol-Containing Biomolecules.

    PubMed

    Rollin-Genetet, Françoise; Seidel, Caroline; Artells, Ester; Auffan, Mélanie; Thiéry, Alain; Vidaud, Claude

    2015-12-21

    The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine-cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce(4+)/Ce(3+) redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce(3+) disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules.

  12. Formation of reactive oxygen species by human and bacterial pyruvate and 2-oxoglutarate dehydrogenase multienzyme complexes reconstituted from recombinant components

    PubMed Central

    Ambrus, Attila; Nemeria, Natalia S.; Torocsik, Beata; Tretter, Laszlo; Nilsson, Mattias; Jordan, Frank; Adam-Vizi, Vera

    2015-01-01

    Individual recombinant components of pyruvate and 2-oxoglutarate dehydrogenase multienzyme complexes (PDHc, OGDHc) of human and Escherichia coli (E. coli) origin were expressed and purified from E. coli with optimized protocols. The four multienzyme complexes were each reconstituted under optimal conditions at different stoichiometric ratios. Binding stoichiometries for the highest catalytic efficiency were determined from the rate of NADH generation by the complexes at physiological pH. Since some of these complexes were shown to possess ‘moonlighting’ activities under pathological conditions often accompanied by acidosis, activities were also determined at pH 6.3. As reactive oxygen species (ROS) generation by the E3 component of hOGDHc is a pathologically relevant feature, superoxide generation by the complexes with optimal stoichiometry was measured by the acetylated cytochrome c reduction method in both the forward and the reverse catalytic directions. Various known affectors of physiological activity and ROS production, including Ca2+, ADP, lipoylation status or pH, were investigated. The human complexes were also reconstituted with the most prevalent human pathological mutant of the E3 component, G194C and characterized; isolated human E3 with the G194C substitution was previously reported to have an enhanced ROS generating capacity. It is demonstrated that: i. PDHc, similarly to OGDHc, is able to generate ROS and this feature is displayed by both the E. coli and human complexes, ii. Reconstituted hPDHc generates ROS at a significantly higher rate as compared to hOGDHc in both the forward and the reverse reactions when ROS generation is calculated for unit mass of their common E3 component, iii. The E1 component or E1-E2 subcomplex generates significant amount of ROS only in hOGDHc; iv. Incorporation of the G194C variant of hE3, the result of a disease-causing mutation, into reconstituted hOGDHc and hPDHc indeed leads to a decreased activity of both

  13. Formation of reactive oxygen species by human and bacterial pyruvate and 2-oxoglutarate dehydrogenase multienzyme complexes reconstituted from recombinant components.

    PubMed

    Ambrus, Attila; Nemeria, Natalia S; Torocsik, Beata; Tretter, Laszlo; Nilsson, Mattias; Jordan, Frank; Adam-Vizi, Vera

    2015-12-01

    Individual recombinant components of pyruvate and 2-oxoglutarate dehydrogenase multienzyme complexes (PDHc, OGDHc) of human and Escherichia coli (E. coli) origin were expressed and purified from E. coli with optimized protocols. The four multienzyme complexes were each reconstituted under optimal conditions at different stoichiometric ratios. Binding stoichiometries for the highest catalytic efficiency were determined from the rate of NADH generation by the complexes at physiological pH. Since some of these complexes were shown to possess 'moonlighting' activities under pathological conditions often accompanied by acidosis, activities were also determined at pH 6.3. As reactive oxygen species (ROS) generation by the E3 component of hOGDHc is a pathologically relevant feature, superoxide generation by the complexes with optimal stoichiometry was measured by the acetylated cytochrome c reduction method in both the forward and the reverse catalytic directions. Various known affectors of physiological activity and ROS production, including Ca(2+), ADP, lipoylation status or pH, were investigated. The human complexes were also reconstituted with the most prevalent human pathological mutant of the E3 component, G194C and characterized; isolated human E3 with the G194C substitution was previously reported to have an enhanced ROS generating capacity. It is demonstrated that: i. PDHc, similarly to OGDHc, is able to generate ROS and this feature is displayed by both the E. coli and human complexes, ii. Reconstituted hPDHc generates ROS at a significantly higher rate as compared to hOGDHc in both the forward and the reverse reactions when ROS generation is calculated for unit mass of their common E3 component, iii. The E1 component or E1-E2 subcomplex generates significant amount of ROS only in hOGDHc; iv. Incorporation of the G194C variant of hE3, the result of a disease-causing mutation, into reconstituted hOGDHc and hPDHc indeed leads to a decreased activity of both

  14. Reactive overprint of the Central Indian Ridge mantle and formation of hybrid troctolites: reassessing the significance of bulk oceanic crust

    NASA Astrophysics Data System (ADS)

    Sanfilippo, A.; Morishita, T.; Kumagai, H.; Nakamura, K.; Okino, K.; Tamura, A.; Arai, S.

    2014-12-01

    The idea that hybridized mantle rocks can contribute to the oceanic crust composition has recently emerged thanks to studies on primitive (olivine-rich) troctolites [e.g. 1]. These rocks are considered to be formed by melt-rock interaction, but the exact reaction process by which they originate is still debated and their role on the bulk oceanic crust composition has been never defined. Olivine-rich troctolites have been mostly found at slow spreading ridges [2] or at their fossil analogues [3]. Similar rocks have been recently collected in the 25ºS area of the intermediate spreading Central Indian Ridge (CIR), and rarely characterize the crust mantle boundary at fast spreading ridges [4]. We show that textural and chemical inheritances of the pre-existing mantle are preserved in the CIR troctolites. In particular, the local occurrence of granular, mantle-derived orthopyroxenes and the composition of the associated clinopyroxene indicate that these crustal rocks formed through a direct (one-stage) conversion of a mantle peridotite. We use chemical evidence to infer the same origin of the olivine-rich troctolites worldwide, concluding that the reactive overprint of the oceanic mantle is a process diffused over the entire spreading rate spectrum. Bulk oceanic crust estimates of the Hess Deep (Pacific) and Atlantis Massif (Atlantic) crustal sections are used to quantify and compare the effect of these rocks on the bulk crust composition at fast and slow spreading ridges. Our inferences suggest that the significance of the bulk oceanic crust should be reassessed. When hybrid troctolites are included at crustal levels, the oceanic crust cannot be considered equal to the composition of the melt extracted from the mantle, but it results more primitive and importantly thicker. References: [1] Suhr G., Hellebrand E., Johnson K., Brunelli D., 2008, Geochem. Geophys. Geosyst. 9, doi:10.1029/2008GC002012; [2] Drouin M., Godard M., Ildefonse B., Bruguier O., Garrido C

  15. Mechanisms of the formation of low spatial frequency LIPSS on Ni/  Ti reactive multilayers

    NASA Astrophysics Data System (ADS)

    Cangueiro, Liliana T.; Cavaleiro, André J.; Morgiel, Jerzy; Vilar, Rui

    2016-09-01

    The present paper aims at investigating the mechanisms of imprinting LIPSS (laser-induced periodic surface structures), arrangements of parallel ripples with a periodicity slightly smaller than the radiation wavelength, on metallic surfaces. To this end, Ni/Ti multi-layered samples produced by magnetron sputtering were textured with LIPSS using a 1030 nm, 560 fs pulse duration laser and pulse frequency of 1 kHz, and the resulting surfaces were investigated by scanning and transmission electron microscopies. The results obtained show that the core of the ripples remains in the solid state during the laser treatment, except for a layer of material about 30 nm thick at the valleys and 65-130 nm thick at the top of the crests, which melts and solidifies forming NiTi with an amorphous structure. A layer of ablation debris composed of amorphous NiTi nanoparticles was redeposited on the LIPSS crests. The results achieved indicate that the periodic variation of the absorbed radiation intensity leads to a variation of the predominant ablation mechanisms and, consequently, of the ablation rate, thus explaining the rippled surface topography. The comparison with theoretical predictions suggests that in the intensity maxima (corresponding to the valleys) the material is removed by liquid spallation, while at its minima (the crests) the predominant material removal mechanism is melting and vaporization. These results support Sipe et al LIPSS formation theory and are in contradiction with the theories that explain the formation of LIPSS by convective fluid flow or self-organized mass transport of a laser-induced instability.

  16. Cryptotanshinone inhibits TNF-α-induced LOX-1 expression by suppressing reactive oxygen species (ROS) formation in endothelial cells.

    PubMed

    Ran, Xiaoli; Zhao, Wenwen; Li, Wenping; Shi, Jingshan; Chen, Xiuping

    2016-07-01

    Cryptotanshinone (CPT) is a natural compound isolated from traditional Chinese medicine Salvia miltiorrhiza Bunge. In the present study, the regulatory effect and potential mechanisms of CPT on tumor necrosis factor alpha (TNF-α) induced lectin-like receptor for oxidized low density lipoprotein (LOX-1) were investigated. Human umbilical vein endothelial cells (HUVECs) were cultured and the effect of TNF-α on LOX-1 expression at mRNA and protein levels was determined by Real-time PCR and Western blotting respectively. The formation of intracellular ROS was determined with fluorescence probe CM-DCFH2-DA. The endothelial ox-LDL uptake was evaluated with DiI-ox-LDL. The effect of CPT on LOX-1 expression was also evaluated with SD rats. TNF-α induced LOX-1 expression in a dose- and time-dependent manner in endothelial cells. TNF-α induced ROS formation, phosphorylation of NF-κB p65 and ERK, and LOX-1 expression, which were suppressed by rotenone, DPI, NAC, and CPT. NF-κB inhibitor BAY11-7082 and ERK inhibitor PD98059 inhibited TNF-α-induced LOX-1 expression. CPT and NAC suppressed TNF-α-induced LOX-1 expression and phosphorylation of NF-κB p65 and ERK in rat aorta. These data suggested that TNF-α induced LOX-1 expression via ROS activated NF-κB/ERK pathway, which could be inhibited by CPT. This study provides new insights for the anti-atherosclerotic effect of CPT.

  17. Insights into the photo-induced formation of reactive intermediates from effluent organic matter: The role of chemical constituents.

    PubMed

    Zhou, Huaxi; Lian, Lushi; Yan, Shuwen; Song, Weihua

    2017-04-01

    In the present study, the formation of triplet states of organic matters ((3)OM(∗)) from effluent organic matter (EfOM) under simulated solar irradiation was investigated. EfOM was separated into hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) components. The quantum yield coefficients (ƒTMP) of (3)OM(∗) were measured for each component and compared to those of reference natural organic matter (NOM). NaBH4 reduction was performed on the EfOM, and the effect of aromatic ketones moieties on triplet formation was also determined. Furthermore, the apparent quantum yield of (1)O2 (Φ1O2) and O2(•-) (ΦO2•-) was measured. Our results suggested that the HPI fraction acted as a sink for (3)OM(∗). A linear correlation was observed between ƒTMP and Φ1O2 for NOM/EfOM, except for NaBH4-reduced effluent and HPI components. Both ƒTMP and Φ1O2 were positively correlated with the contribution rates of NaBH4-reducible moieties (aromatic ketones) toward (3)OM(∗). Aromatic ketones were primarily responsible for the production of (3)OM(∗) from EfOM, whereas quinone moieties played a key role in the production of (3)OM(∗) in NOM-enriched solutions. Understanding the role of chemical constituents on the photo activity of EfOM/NOM is essential for providing useful insights on their photochemical effects in aquatic systems.

  18. Cryptotanshinone inhibits TNF-α-induced LOX-1 expression by suppressing reactive oxygen species (ROS) formation in endothelial cells

    PubMed Central

    Ran, Xiaoli; Zhao, Wenwen; Li, Wenping

    2016-01-01

    Cryptotanshinone (CPT) is a natural compound isolated from traditional Chinese medicine Salvia miltiorrhiza Bunge. In the present study, the regulatory effect and potential mechanisms of CPT on tumor necrosis factor alpha (TNF-α) induced lectin-like receptor for oxidized low density lipoprotein (LOX-1) were investigated. Human umbilical vein endothelial cells (HUVECs) were cultured and the effect of TNF-α on LOX-1 expression at mRNA and protein levels was determined by Real-time PCR and Western blotting respectively. The formation of intracellular ROS was determined with fluorescence probe CM-DCFH2-DA. The endothelial ox-LDL uptake was evaluated with DiI-ox-LDL. The effect of CPT on LOX-1 expression was also evaluated with SD rats. TNF-α induced LOX-1 expression in a dose- and time-dependent manner in endothelial cells. TNF-α induced ROS formation, phosphorylation of NF-κB p65 and ERK, and LOX-1 expression, which were suppressed by rotenone, DPI, NAC, and CPT. NF-κB inhibitor BAY11-7082 and ERK inhibitor PD98059 inhibited TNF-α-induced LOX-1 expression. CPT and NAC suppressed TNF-α-induced LOX-1 expression and phosphorylation of NF-κB p65 and ERK in rat aorta. These data suggested that TNF-α induced LOX-1 expression via ROS activated NF-κB/ERK pathway, which could be inhibited by CPT. This study provides new insights for the anti-atherosclerotic effect of CPT. PMID:27382351

  19. CO J = 2-1 LINE EMISSION IN CLUSTER GALAXIES AT z {approx} 1: FUELING STAR FORMATION IN DENSE ENVIRONMENTS

    SciTech Connect

    Wagg, Jeff; Pope, Alexandra; Alberts, Stacey; Armus, Lee; Desai, Vandana; Brodwin, Mark; Bussmann, Robert S.; Dey, Arjun; Jannuzi, Buell; Le Floc'h, Emeric; Melbourne, Jason; Stern, Daniel

    2012-06-20

    We present observations of CO J = 2-1 line emission in infrared-luminous cluster galaxies at z {approx} 1 using the IRAM Plateau de Bure Interferometer. Our two primary targets are optically faint, dust-obscured galaxies (DOGs) found to lie within 2 Mpc of the centers of two massive (>10{sup 14} M{sub Sun }) galaxy clusters. CO line emission is not detected in either DOG. We calculate 3{sigma} upper limits to the CO J = 2-1 line luminosities, L'{sub CO} < 6.08 Multiplication-Sign 10{sup 9} and <6.63 Multiplication-Sign 10{sup 9} K km s{sup -1} pc{sup 2}. Assuming a CO-to-H{sub 2} conversion factor derived for ultraluminous infrared galaxies in the local universe, this translates to limits on the cold molecular gas mass of M{sub H{sub 2}}< 4.86 Multiplication-Sign 10{sup 9} M{sub Sun} and M{sub H{sub 2}}< 5.30 Multiplication-Sign 10{sup 9} M{sub Sun }. Both DOGs exhibit mid-infrared continuum emission that follows a power law, suggesting that an active galactic nucleus (AGN) contributes to the dust heating. As such, estimates of the star formation efficiencies in these DOGs are uncertain. A third cluster member with an infrared luminosity, L{sub IR} < 7.4 Multiplication-Sign 10{sup 11} L{sub Sun }, is serendipitously detected in CO J = 2-1 line emission in the field of one of the DOGs located roughly two virial radii away from the cluster center. The optical spectrum of this object suggests that it is likely an obscured AGN, and the measured CO line luminosity is L'{sub CO} = (1.94 {+-} 0.35) Multiplication-Sign 10{sup 10} K km s{sup -1} pc{sup 2}, which leads to an estimated cold molecular gas mass M{sub H{sub 2}}= (1.55{+-}0.28) Multiplication-Sign 10{sup 10} M{sub Sun }. A significant reservoir of molecular gas in a z {approx} 1 galaxy located away from the cluster center demonstrates that the fuel can exist to drive an increase in star formation and AGN activity at the outskirts of high-redshift clusters.

  20. Role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium deposits: insights from reactive-flow modeling

    NASA Astrophysics Data System (ADS)

    Aghbelagh, Yousef Beiraghdar; Yang, Jianwen

    2017-03-01

    The role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium (URU) deposits in sedimentary basins during tectonically quiet periods is investigated. A number of reactive-flow modeling experiments at the deposit scale were carried out by assigning different dip angles and directions to a fault and various permeabilities to hydrostratigraphic units). The results show that the fault dip angle and direction, and permeability of the hydrostratigraphic units govern the convection pattern, temperature distribution, and uranium mineralization. A vertical fault results in uranium mineralization at the bottom of the fault within the basement, while a dipping fault leads to precipitation of uraninite below the unconformity either away from or along the plane of the fault, depending on the fault permeability. A more permeable fault causes uraninite precipitates along the fault plane, whereas a less permeable one gives rise to the precipitation of uraninite away from it. No economic ore mineralization can form when either very low or very high permeabilities are assigned to the sandstone or basement suggesting that these units seem to have an optimal window of permeability for the formation of uranium deposits. Physicochemical parameters also exert an additional control in both the location and grade of URU deposits. These results indicate that the difference in size and grade of different URU deposits may result from variation in fluid flow pattern and physicochemical conditions, caused by the change in structural features and hydraulic properties of the stratigraphic units involved.

  1. Role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium deposits: insights from reactive-flow modeling

    NASA Astrophysics Data System (ADS)

    Aghbelagh, Yousef Beiraghdar; Yang, Jianwen

    2016-11-01

    The role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium (URU) deposits in sedimentary basins during tectonically quiet periods is investigated. A number of reactive-flow modeling experiments at the deposit scale were carried out by assigning different dip angles and directions to a fault and various permeabilities to hydrostratigraphic units). The results show that the fault dip angle and direction, and permeability of the hydrostratigraphic units govern the convection pattern, temperature distribution, and uranium mineralization. A vertical fault results in uranium mineralization at the bottom of the fault within the basement, while a dipping fault leads to precipitation of uraninite below the unconformity either away from or along the plane of the fault, depending on the fault permeability. A more permeable fault causes uraninite precipitates along the fault plane, whereas a less permeable one gives rise to the precipitation of uraninite away from it. No economic ore mineralization can form when either very low or very high permeabilities are assigned to the sandstone or basement suggesting that these units seem to have an optimal window of permeability for the formation of uranium deposits. Physicochemical parameters also exert an additional control in both the location and grade of URU deposits. These results indicate that the difference in size and grade of different URU deposits may result from variation in fluid flow pattern and physicochemical conditions, caused by the change in structural features and hydraulic properties of the stratigraphic units involved.

  2. Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

    PubMed

    Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

    2000-12-01

    towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.

  3. Substrate-promoted formation of a catalytically competent binuclear center and regulation of reactivity in a glycerophosphodiesterase from Enterobacter aerogenes.

    PubMed

    Hadler, Kieran S; Tanifum, Eric A; Yip, Sylvia Hsu-Chen; Mitić, Natasa; Guddat, Luke W; Jackson, Colin J; Gahan, Lawrence R; Nguyen, Kelly; Carr, Paul D; Ollis, David L; Hengge, Alvan C; Larrabee, James A; Schenk, Gerhard

    2008-10-29

    The glycerophosphodiesterase (GpdQ) from Enterobacter aerogenes is a promiscuous binuclear metallohydrolase that catalyzes the hydrolysis of mono-, di-, and triester substrates, including some organophosphate pesticides and products of the degradation of nerve agents. GpdQ has attracted recent attention as a promising enzymatic bioremediator. Here, we have investigated the catalytic mechanism of this versatile enzyme using a range of techniques. An improved crystal structure (1.9 A resolution) illustrates the presence of (i) an extended hydrogen bond network in the active site, and (ii) two possible nucleophiles, i.e., water/hydroxide ligands, coordinated to one or both metal ions. While it is at present not possible to unambiguously distinguish between these two possibilities, a reaction mechanism is proposed whereby the terminally bound H2O/OH(-) acts as the nucleophile, activated via hydrogen bonding by the bridging water molecule. Furthermore, the presence of substrate promotes the formation of a catalytically competent binuclear center by significantly enhancing the binding affinity of one of the metal ions in the active site. Asn80 appears to display coordination flexibility that may modulate enzyme activity. Kinetic data suggest that the rate-limiting step occurs after hydrolysis, i.e., the release of the phosphate moiety and the concomitant dissociation of one of the metal ions and/or associated conformational changes. Thus, it is proposed that GpdQ employs an intricate regulatory mechanism for catalysis, where coordination flexibility in one of the two metal binding sites is essential for optimal activity.

  4. Formation of a long-lived electron-transfer state in mesoporous silica-alumina composites enhances photocatalytic oxygenation reactivity

    PubMed Central

    Fukuzumi, Shunichi; Doi, Kaoru; Itoh, Akinori; Suenobu, Tomoyoshi; Ohkubo, Kei; Yamada, Yusuke; Karlin, Kenneth D.

    2012-01-01

    A simple donor-acceptor linked dyad, 9-mesityl-10-methylacridinium ion (Acr+-Mes) was incorporated into nanosized mesoporous silica-alumina to form a composite, which in acetonitrile is highly dispersed. In this medium, upon visible light irradiation, the formation of an extremely long-lived electron-transfer state (Acr•-Mes•+) was confirmed by EPR and laser flash photolysis spectroscopic methods. The composite of Acr+-Mes-incorporated mesoporous silica-alumina with an added copper complex [(tmpa)CuII] (tmpa = tris(2-pyridylmethyl)amine) acts as an efficient and robust photocatalyst for the selective oxygenation of p-xylene by molecular oxygen to produce p-tolualdehyde and hydrogen peroxide. Thus, incorporation of Acr+-Mes into nanosized mesoporous silica-alumina combined with an O2-reduction catalyst ([(tmpa)CuII]2+) provides a promising method in the development of efficient and robust organic photocatalysts for substrate oxygenation by dioxygen, the ultimate environmentally benign oxidant. PMID:22543164

  5. Atmospheric reactivity of hydroxyl radicals with guaiacol (2-methoxyphenol), a biomass burning emitted compound: Secondary organic aerosol formation and gas-phase oxidation products

    NASA Astrophysics Data System (ADS)

    Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Deboudt, Karine; Fourmentin, Marc; Choël, Marie

    2014-04-01

    Methoxyphenols are low molecular weight semi-volatile polar aromatic compounds produced from the pyrolysis of wood lignin. The reaction of guaiacol (2-methoxyphenol) with hydroxyl radicals has been studied in the LPCA simulation chamber at (294 ± 2) K, atmospheric pressure, low relative humidity (RH < 1%) and under high-NOx conditions using CH3ONO as OH source. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer); the SOA yields were in the range from 0.003 to 0.87 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. Transmission (TEM) and Scanning (SEM) Electron Microscopy observations were performed to characterize the physical state of SOA produced from the OH reaction with guaiacol; they display both liquid and solid particles (in an amorphous state). GC-FID (Gas Chromatography - Flame Ionization Detection) and GC-MS (Gas Chromatography - Mass Spectrometry) analysis show the formation of nitroguaiacol isomers as main oxidation products in the gas- and aerosol-phases. In the gas-phase, the formation yields were (10 ± 2) % for 4-nitroguaiacol (1-hydroxy-2-methoxy-4-nitrobenzene; 4-NG) and (6 ± 2) % for 3- or 6-nitroguaiacol (1-hydroxy-2-methoxy-3-nitrobenzene or 1-hydroxy-2-methoxy-6-nitrobenzene; 3/6-NG; the standards are not commercially available so both isomers cannot be distinguished) whereas in SOA their yield were much lower (≤0.1%). To our knowledge, this work represents the first identification of nitroguaiacols as gaseous oxidation products of the OH reaction with guaiacol. As the reactivity of nitroguaiacols with atmospheric oxidants is probably low, we suggest using them as biomass burning emission gas tracers. The atmospheric implications of the guaiacol + OH reaction are also discussed.

  6. Mitochondrial permeability transition in rat hepatocytes after anoxia/reoxygenation: role of Ca2+-dependent mitochondrial formation of reactive oxygen species.

    PubMed

    Kim, Jae-Sung; Wang, Jin-Hee; Lemasters, John J

    2012-04-01

    Onset of the mitochondrial permeability transition (MPT) is the penultimate event leading to lethal cellular ischemia-reperfusion injury, but the mechanisms precipitating the MPT after reperfusion remain unclear. Here, we investigated the role of mitochondrial free Ca(2+) and reactive oxygen species (ROS) in pH- and MPT-dependent reperfusion injury to hepatocytes. Cultured rat hepatocytes were incubated in anoxic Krebs-Ringer-HEPES buffer at pH 6.2 for 4 h and then reoxygenated at pH 7.4 to simulate ischemia-reperfusion. Some cells were loaded with the Ca(2+) chelators, BAPTA/AM and 2-[(2-bis-[carboxymethyl]aono-5-methoxyphenyl)-methyl-6-methoxy-8-bis[carboxymethyl]aminoquinoline, either by a cold loading protocol for intramitochondrial loading or by warm incubation for cytosolic loading. Cell death was assessed by propidium iodide fluorometry and immunoblotting. Mitochondrial Ca(2+), inner membrane permeability, membrane potential, and ROS formation were monitored with Rhod-2, calcein, tetramethylrhodamine methylester, and dihydrodichlorofluorescein, respectively. Necrotic cell death increased after reoxygenation. Necrosis was blocked by 1 μM cyclosporin A, an MPT inhibitor, and by reoxygenation at pH 6.2. Confocal imaging of Rhod-2, calcein, and dichlorofluorescein revealed that an increase of mitochondrial Ca(2+) and ROS preceded onset of the MPT after reoxygenation. Intramitochondrial Ca(2+) chelation, but not cytosolic Ca(2+) chelation, prevented ROS formation and subsequent necrotic and apoptotic cell death. Reoxygenation with the antioxidants, desferal or diphenylphenylenediamine, also suppressed MPT-mediated cell death. However, inhibition of cytosolic ROS by apocynin or diphenyleneiodonium chloride failed to prevent reoxygenation-induced cell death. In conclusion, Ca(2+)-dependent mitochondrial ROS formation is the molecular signal culminating in onset of the MPT after reoxygenation of anoxic hepatocytes, leading to cell death.

  7. Metabolism of isoniazid by neutrophil myeloperoxidase leads to isoniazid-NAD(+) adduct formation: A comparison of the reactivity of isoniazid with its known human metabolites.

    PubMed

    Khan, Saifur R; Morgan, Andrew G M; Michail, Karim; Srivastava, Nutan; Whittal, Randy M; Aljuhani, Naif; Siraki, Arno G

    2016-04-15

    The formation of isonicotinyl-nicotinamide adenine dinucleotide (INH-NAD(+)) via the mycobacterial catalase-peroxidase enzyme, KatG, has been described as the major component of the mode of action of isoniazid (INH). However, there are numerous human peroxidases that may catalyze this reaction. The role of neutrophil myeloperoxidase (MPO) in INH-NAD(+) adduct formation has never been explored; this is important, as neutrophils are recruited at the site of tuberculosis infection (granuloma) through infected macrophages' cell death signals. In our studies, we showed that neutrophil MPO is capable of INH metabolism using electron paramagnetic resonance (EPR) spin-trapping and UV-Vis spectroscopy. MPO or activated human neutrophils (by phorbol myristate acetate) catalyzed the oxidation of INH and formed several free radical intermediates; the inclusion of superoxide dismutase revealed a carbon-centered radical which is considered to be the reactive metabolite that binds with NAD(+). Other human metabolites, including N-acetyl-INH, N-acetylhydrazine, and hydrazine did not show formation of carbon-centered radicals, and either produced no detectable free radicals, N-centered free radicals, or superoxide, respectively. A comparison of these free radical products indicated that only the carbon-centered radical from INH is reducing in nature, based on UV-Vis measurement of nitroblue tetrazolium reduction. Furthermore, only INH oxidation by MPO led to a new product (λmax=326nm) in the presence of NAD(+). This adduct was confirmed to be isonicotinyl-NAD(+) using LC-MS analysis where the intact adduct was detected (m/z=769). The findings of this study suggest that neutrophil MPO may also play a role in INH pharmacological activity.

  8. Catalytic autothermal reforming increases fuel cell flexibility

    NASA Technical Reports Server (NTRS)

    Flytzani-Stephanopoulos, M.; Voecks, G. E.

    1981-01-01

    Experimental results are presented for the autothermal reforming (ATR) of n-hexane, n-tetradecane, benzene and benzene solutions of naphthalene. The tests were run at atmospheric pressure and at moderately high reactant preheat temperatures in the 800-900 K range. Carbon formation lines were determined for paraffinic and aromatic liquids. Profiles were determined for axial bed temperature and composition. Space velocity efforts were assessed, and the locations and types of carbon were recorded. Significant reactive differences between hydrocarbons were identified. Carbon formation characteristics were hydrocarbon specific. The differing behavior of paraffinic and aromatic fuels with respect to their carbon formation may be important in explaining the narrow range of carbon-free operating conditions found in the ATR of number two fuel oil.

  9. Fuel-rich catalytic combustion of Jet-A fuel-equivalence ratios 5.0 to 8.0

    NASA Technical Reports Server (NTRS)

    Brabbs, Theodore A.; Gracia-Salcedo, Carmen M.

    1989-01-01

    Fuel-rich catalytic combustion (E.R. greater than 5.0) is a unique technique for preheating a hydrocarbon fuel to temperatures much higher than those obtained by conventional heat exchangers. In addition to producing very reactive molecules, the process upgrades the structure of the fuel by the formation of hydrogen and smaller hydrocarbons and produces a cleaner burning fuel by removing some of the fuel carbon from the soot formation chain. With fuel-rich catalytic combustion as the first stage of a two stage combustion system, enhanced fuel properties can be utilized by both high speed engines, where time for ignition and complete combustion is limited, and engines where emission of thermal NO sub x is critical. Two-stage combustion (rich-lean) has been shown to be effective for NO sub x reduction in stationary burners where residence times are long enough to burn-up the soot formed in the first stage. Such residence times are not available in aircraft engines. Thus, the soot-free nature of the present process is critical for high speed engines. The successful application of fuel-rich catalytic combustion to Jet-A, a multicomponent fuel used in gas turbine combustors, is discusssed.

  10. Regulation of macromolecular modulators of urinary stone formation by reactive oxygen species: transcriptional study in an animal model of hyperoxaluria.

    PubMed

    Khan, Saeed R; Joshi, Sunil; Wang, Wei; Peck, Ammon B

    2014-06-01

    We used an unbiased approach of gene expression profiling to determine differential gene expression of all the macromolecular modulators (MMs) considered to be involved in stone formation, in hyperoxaluric rats, with and without treatment with the NADPH oxidase inhibitor apocynin. Male rats were fed rat chow or chow supplemented with 5% wt/wt hydroxy-l-proline (HLP) with or without apocynin-supplemented water. After 28 days, rats were euthanized and their kidneys explanted. Total RNA was isolated and microarray analysis was conducted using the Illumina bead array reader. Gene ontology analysis and the pathway analyses of the genes were done using Database for Annotation, Visualization of Integrated Discovery enrichment analysis tool. Quantitative RT-PCR of selected genes was carried out to verify the microarray results. Expression of selected gene products was confirmed using immunohistochemistry. Administration of HLP led to crystal deposition. Genes encoding for fibronectin, CD 44, fetuin B, osteopontin, and matrix-gla protein were upregulated while those encoding for heavy chains of inter-alpha-inhibitor 1, 3, and 4, calgranulin B, prothrombin, and Tamm-Horsfall protein were downregulated. HLP-fed rats receiving apocynin had a significant reversal in gene expression profiles: those that were upregulated came down while those that were downregulated stepped up. Apocynin treatment resulted in near complete absence of crystals. Clearly, there are two types of MMs; one is downregulated while the other is upregulated during hyperoxaluria and crystal deposition. Apparently gene and protein expressions of known macromolecular modulators of CaOx crystallization are likely regulated by ROS produced in part through the activation of NADPH oxidase.

  11. Reactive Sulfur Species-Mediated Activation of the Keap1-Nrf2 Pathway by 1,2-Naphthoquinone through Sulfenic Acids Formation under Oxidative Stress.

    PubMed

    Shinkai, Yasuhiro; Abiko, Yumi; Ida, Tomoaki; Miura, Takashi; Kakehashi, Hidenao; Ishii, Isao; Nishida, Motohiro; Sawa, Tomohiro; Akaike, Takaaki; Kumagai, Yoshito

    2015-05-18

    Sulfhydration by a hydrogen sulfide anion and electrophile thiolation by reactive sulfur species (RSS) such as persulfides/polysulfides (e.g., R-S-SH/R-S-Sn-H(R)) are unique reactions in electrophilic signaling. Using 1,2-dihydroxynaphthalene-4-thioacetate (1,2-NQH2-SAc) as a precursor to 1,2-dihydroxynaphthalene-4-thiol (1,2-NQH2-SH) and a generator of reactive oxygen species (ROS), we demonstrate that protein thiols can be modified by a reactive sulfenic acid to form disulfide adducts that undergo rapid cleavage in the presence of glutathione (GSH). As expected, 1,2-NQH2-SAc is rapidly hydrolyzed and partially oxidized to yield 1,2-NQ-SH, resulting in a redox cycling reaction that produces ROS through a chemical disproportionation reaction. The sulfenic acid forms of 1,2-NQ-SH and 1,2-NQH2-SH were detected by derivatization experiments with dimedone. 1,2-NQH2-SOH modified Keap1 at Cys171 to produce a Keap1-S-S-1,2-NQH2 adduct. Subsequent exposure of A431 cells to 1,2-NQ or 1,2-NQH2-SAc caused an extensive chemical modification of cellular proteins in both cases. Protein adduction by 1,2-NQ through a thio ether (C-S-C) bond slowly declined through a GSH-dependent S-transarylation reaction, whereas that originating from 1,2-NQH2-SAc through a disulfide (C-S-S-C) bond was rapidly restored to the free protein thiol in the cells. Under these conditions, 1,2-NQH2-SAc activated Nrf2 and upregulated its target genes, which were enhanced by pretreatment with buthionine sulfoximine (BSO), to deplete cellular GSH. Pretreatment of catalase conjugated with poly(ethylene glycol) suppressed Nrf2 activation by 1,2-NQH2-SAc. These results suggest that RSS-mediated reversible electrophilic signaling takes place through sulfenic acids formation under oxidative stress.

  12. Fuel flexible fuel injector

    DOEpatents

    Tuthill, Richard S; Davis, Dustin W; Dai, Zhongtao

    2015-02-03

    A disclosed fuel injector provides mixing of fuel with airflow by surrounding a swirled fuel flow with first and second swirled airflows that ensures mixing prior to or upon entering the combustion chamber. Fuel tubes produce a central fuel flow along with a central airflow through a plurality of openings to generate the high velocity fuel/air mixture along the axis of the fuel injector in addition to the swirled fuel/air mixture.

  13. Reactivity of San Andres dolomite

    SciTech Connect

    Anderson, M.S. )

    1991-05-01

    The San Andres formation is routinely stimulated with acid. Although numerous acidizing simulators are available to aid in treatment optimization, existing reactivity data were generated with quarried rock rather than formation samples. This paper presents reactivity data for five San Andres dolomite samples. These data can be used in most fracture-acidizing-design simulators to allow more accurate simulation of the acidizing process.

  14. Central role of endogenous Toll-like receptor-2 activation in regulating inflammation, reactive oxygen species production, and subsequent neointimal formation after vascular injury

    SciTech Connect

    Shishido, Tetsuro . E-mail: Tetsuro_Shishido@URMC.Rochester.edu; Nozaki, Naoki; Takahashi, Hiroki; Arimoto, Takanori; Niizeki, Takeshi; Koyama, Yo; Abe, Jun-ichi; Takeishi, Yasuchika; Kubota, Isao

    2006-07-14

    Background: It is now evident that inflammation after vascular injury has significant impact on the restenosis after revascularization procedures such as angioplasty, stenting, and bypass grafting. However, the mechanisms that regulate inflammation and repair after vascular injury are incompletely understood. Here, we report that vascular injury-mediated cytokine expression, reactive oxygen species (ROS) production, as well as subsequent neointimal formation requires Toll-like receptor-2 (TLR-2) mediated signaling pathway in vivo. Methods and results: Vascular injury was induced by cuff-placement around the femoral artery in non-transgenic littermates (NLC) and TLR-2 knockout (TLR-2KO) mice. After cuff-placement in NLC mice, expression of TLR-2 was significantly increased in both smooth muscle medial layer and adventitia. Interestingly, we found that inflammatory genes expression such as tumor necrosis factor-{alpha}, interleukin-1{beta} (IL-1{beta}), IL-6, and monocyte chemoattractant protein-1 were markedly decreased in TLR-2KO mice compared with NLC mice. In addition, ROS production after vascular injury was attenuated in TLR-2KO mice compared with NLC mice. Since we observed the significant role of endogenous TLR-2 activation in regulating inflammatory responses and ROS production after vascular injury, we determined whether inhibition of endogenous TLR-2 activation can inhibit neointimal proliferation after vascular injury. Neointimal hyperplasia was markedly suppressed in TLR-2KO mice compared with WT mice at both 2 and 4 weeks after vascular injury. Conclusions: These findings suggested that endogenous TLR-2 activation might play a central role in the regulation of vascular inflammation as well as subsequent neointimal formation in injured vessels.

  15. Formation of reactive aldehydes (MDA, HHE, HNE) during the digestion of cod liver oil: comparison of human and porcine in vitro digestion models.

    PubMed

    Tullberg, Cecilia; Larsson, Karin; Carlsson, Nils-Gunnar; Comi, Irene; Scheers, Nathalie; Vegarud, Gerd; Undeland, Ingrid

    2016-03-01

    In this work, we investigated lipid oxidation of cod liver oil during gastrointestinal (GI) digestion using two types of in vitro digestion models. In the first type of model, we used human GI juices, while we used digestive enzymes and bile from porcine origin in the second type of model. Human and porcine models were matched with respect to factors important for lipolysis, using a standardized digestion protocol. The digests were analysed for reactive oxidation products: malondialdehyde (MDA), 4-hydroxy-trans-2-nonenal (HNE), and 4-hydroxy-trans-2-hexenal (HHE) by liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (LC/APCI-MS), and for free fatty acids (FFA) obtained during the digestion by gas chromatography-mass spectrometry (GC-MS). The formation of the oxidation products MDA, HHE, and HNE was low during the gastric digestion, however, it increased during the duodenal digestion. The formation of the oxidation products reached higher levels when digestive juices of human origin were used (60 μM of MDA, 0.96 μM of HHE, and 1.6 μM of HNE) compared to when using enzymes and bile of porcine origin (9.8, and 0.36 μM of MDA; 0.16, and 0.026 μM of HHE; 0.23, and 0.005 μM of HNE, respectively, in porcine models I and II). In all models, FFA release was only detected during the intestinal step, and reached up to 31% of total fatty acids (FA). The findings in this work may be of importance when designing oxidation oriented lipid digestion studies.

  16. UV-B Induced Generation of Reactive Oxygen Species Promotes Formation of BFA-Induced Compartments in Cells of Arabidopsis Root Apices

    PubMed Central

    Yokawa, Ken; Kagenishi, Tomoko; Baluška, František

    2016-01-01

    UV-B radiation is an important part of the electromagnetic spectrum emitted by the sun. For much of the period of biological evolution organisms have been exposed to UV radiation, and have developed diverse mechanisms to cope with this potential stress factor. Roots are usually shielded from exposure to UV by the surrounding soil, but may nevertheless be exposed to high energy radiation on the soil surface. Due to their high sensitivity to UV-B radiation, plant roots need to respond rapidly in order to minimize exposure on the surface. In addition to root gravitropism, effective light perception by roots has recently been discovered to be essential for triggering negative root phototropism in Arabidopsis. However, it is not fully understood how UV-B affects root growth and phototropism. Here, we report that UV-B induces rapid generation of reactive oxygen species which in turn promotes the formation of BFA-induced compartments in the Arabidopsis root apex. During unilateral UV-B irradiation of roots changes in auxin concentration on the illuminated side have been recorded. In conclusion, UV-B-induced and ROS-mediated stimulation of vesicle recycling promotes root growth and induces negative phototropism. PMID:26793199

  17. A newly discovered oxidant defence system and its involvement in the development of Aurelia aurita (Scyphozoa, Cnidaria): reactive oxygen species and elemental iodine control medusa formation.

    PubMed

    Berking, Stefan; Czech, Nicole; Gerharz, Melanie; Herrmann, Klaus; Hoffmann, Uwe; Raifer, Hartmann; Sekul, Guy; Siefker, Barbara; Sommerei, Andrea; Vedder, Fritz

    2005-01-01

    In Aurelia aurita, applied iodine induces medusa formation (strobilation). This process also occurs when the temperature is lowered. This was found to increase oxidative stress resulting in an increased production of iodine from iodide. One polyp produces several medusae (initially termed ephyrae) starting at the polyp's oral end. The spreading of strobilation down the body column is controlled by a feedback loop: ephyra anlagen decrease the tyrosine content in adjacent polyp tissue by producing melanin from tyrosine. Endogenous tyrosine is able to remove iodine by forming iodiferous tyrosine compounds. The reduced level of tyrosine causes the ephyra-polyp-border to move towards the basal end of the former polyp. We argue that an oxidant defence system may exist which makes use of iodide and tyrosine. Like other marine invertebrates, polyps of Aurelia contain iodide ions. Inevitably produced peroxides oxidise iodide into iodine. The danger to be harmed by iodine is strongly decreased by endogenous tyrosine which reacts with iodine to form iodiferous tyrosine compounds including thyroxin. Both substances together, iodide and tyrosine, form an efficient oxidant defence system which shields the tissue against damage by reactive oxygen species. In the course of evolution (from a species at the basis of the animal kingdom like Aurelia to a highly evolved species like man) the waste product thyroxin (indicating a high metabolic rate) has developed into a hormone which controls the metabolic rate.

  18. μ-Opioid modulation in the rostral solitary nucleus and reticular formation alters taste reactivity: evidence for a suppressive effect on consummatory behavior

    PubMed Central

    Travers, Susan P.

    2011-01-01

    The neural control of feeding involves many neuromodulators, including the endogenous opioids that bind μ-opioid receptors (MORs). Injections of the MOR agonist, Damgo, into limbic and hypothalamic forebrain sites increase intake, particularly of palatable foods. Indeed, forebrain Damgo injections increase sucrose-elicited licking but reduce aversive responding (gaping) to quinine, suggesting that MOR activation may enhance taste palatability. A μ-opioid influence on taste reactivity has not been assessed in the brain stem. However, MORs are present in the first-order taste relay, the rostral nucleus of the solitary tract (rNST), and in the immediately subjacent reticular formation (RF), a region known to be essential for consummatory responses. Thus, to evaluate the consequences of rNST/dorsal RF Damgo in this region, we implanted rats with intraoral cannulas, electromyographic electrodes, and brain cannulas aimed at the ventral border of the rNST. Licking and gaping elicited with sucrose, water, and quinine were assessed before and after intramedullary Damgo and saline infusions. Damgo slowed the rate, increased the amplitude, and decreased the size of fluid-induced lick and gape bouts. In addition, the neutral stimulus water, which typically elicits licks, began to evoke gapes. Thus, the current results demonstrate that μ-opioid activation in the rNST/dorsal RF exerts complex effects on oromotor responding that contrast with forebrain effects and are more indicative of a suppressive, rather than a facilitatory effect on ingestion. PMID:21697523

  19. Reactive Oxygen Species Formation and Apoptosis in Human Peripheral Blood Mononuclear Cell Induced by 900 MHz Mobile Phone Radiation

    PubMed Central

    Lu, Yao-Sheng; Huang, Bao-Tian; Huang, Yao-Xiong

    2012-01-01

    We demonstrate that reactive oxygen species (ROS) plays an important role in the process of apoptosis in human peripheral blood mononuclear cell (PBMC) which is induced by the radiation of 900 MHz radiofrequency electromagnetic field (RFEMF) at a specific absorption rate (SAR) of ~0.4 W/kg when the exposure lasts longer than two hours. The apoptosis is induced through the mitochondrial pathway and mediated by activating ROS and caspase-3, and decreasing the mitochondrial potential. The activation of ROS is triggered by the conformation disturbance of lipids, protein, and DNA induced by the exposure of GSM RFEMF. Although human PBMC was found to have a self-protection mechanism of releasing carotenoid in response to oxidative stress to lessen the further increase of ROS, the imbalance between the antioxidant defenses and ROS formation still results in an increase of cell death with the exposure time and can cause about 37% human PBMC death in eight hours. PMID:22778799

  20. Conformational changes at the highly reactive cystein and lysine regions of skeletal muscle myosin induced by formation of transition state analogues.

    PubMed

    Maruta, S; Homma, K; Ohki, T

    1998-09-01

    Myosin forms stable ternary complexes with Mg2+-ADP and phosphate analogues of aluminum fluoride (AlF4-), beryllium fluoride (BeFn), and scandium fluoride (ScFn). These complexes are distinct from each other and may mimic different transient states in the ATPase cycle [Maruta et al. (1993) J. Biol. Chem. 268, 7093-7100]. Regions of skeletal muscle myosin containing the highly reactive residues Cys 707 (SH1), Cys 697 (SH2), and lysine 83 (RLR) dramatically alter their local conformation when myosin hydrolyzes ATP, and these changes may reflect formation of a series of transient intermediates during ATP hydrolysis. We used the fluorescent probes 4-fluoro-7-sulfamoylbezofurazan, 2-(4'-maleimidylanilino)naphthalene-6-sulfonic acid, and trinitrobenzene-sulfonate, which bind to SH1, SH2, and RLR, respectively, to examine differences in local conformations within myosin.ADP.phosphate analogue (BeFn, Vi, AlF4-, and ScFn) complexes. It was observed that the ternary complexes had SH1 conformations similar to those seen on S-1 in the presence of ATP. In contrast, local conformations in the SH2 and RLR regions of S-1.ADP.BeFn were different from those in corresponding regions of S-1.ADP.AlF4- or ScFn. These results suggest that SH1 and SH2 move distinctly during ATP hydrolysis and that the local conformations of the SH2 and RLR regions more sensitively reflect different transient states.

  1. JAK2V617F leads to intrinsic changes in platelet formation and reactivity in a knock-in mouse model of essential thrombocythemia

    PubMed Central

    Hobbs, Catherine M.; Manning, Harriet; Bennett, Cavan; Vasquez, Louella; Severin, Sonia; Brain, Lauren; Mazharian, Alexandra; Guerrero, Jose A.; Li, Juan; Soranzo, Nicole; Green, Anthony R.; Watson, Steve P.

    2013-01-01

    The principal morbidity and mortality in patients with essential thrombocythemia (ET) and polycythemia rubra vera (PV) stems from thrombotic events. Most patients with ET/PV harbor a JAK2V617F mutation, but its role in the thrombotic diathesis remains obscure. Platelet function studies in patients are difficult to interpret because of interindividual heterogeneity, reflecting variations in the proportion of platelets derived from the malignant clone, differences in the presence of additional mutations, and the effects of medical treatments. To circumvent these issues, we have studied a JAK2V617F knock-in mouse model of ET in which all megakaryocytes and platelets express JAK2V617F at a physiological level, equivalent to that present in human ET patients. We show that, in addition to increased differentiation, JAK2V617F-positive megakaryocytes display greater migratory ability and proplatelet formation. We demonstrate in a range of assays that platelet reactivity to agonists is enhanced, with a concomitant increase in platelet aggregation in vitro and a reduced duration of bleeding in vivo. These data suggest that JAK2V617F leads to intrinsic changes in both megakaryocyte and platelet biology beyond an increase in cell number. In support of this hypothesis, we identify multiple differentially expressed genes in JAK2V617F megakaryocytes that may underlie the observed biological differences. PMID:24085768

  2. Hydrogen Sulfide Prevents Formation of Reactive Oxygen Species through PI3K/Akt Signaling and Limits Ventilator-Induced Lung Injury

    PubMed Central

    Spassov, Sashko Georgiev; Donus, Rosa; Ihle, Paul Mikael; Engelstaedter, Helen; Hoetzel, Alexander

    2017-01-01

    The development of ventilator-induced lung injury (VILI) is still a major problem in mechanically ventilated patients. Low dose inhalation of hydrogen sulfide (H2S) during mechanical ventilation has been proven to prevent lung damage by limiting inflammatory responses in rodent models. However, the capacity of H2S to affect oxidative processes in VILI and its underlying molecular signaling pathways remains elusive. In the present study we show that ventilation with moderate tidal volumes of 12 ml/kg for 6 h led to an excessive formation of reactive oxygen species (ROS) in mice lungs which was prevented by supplemental inhalation of 80 parts per million of H2S. In addition, phosphorylation of the signaling protein Akt was induced by H2S. In contrast, inhibition of Akt by LY294002 during ventilation reestablished lung damage, neutrophil influx, and proinflammatory cytokine release despite the presence of H2S. Moreover, the ability of H2S to induce the antioxidant glutathione and to prevent ROS production was reversed in the presence of the Akt inhibitor. Here, we provide the first evidence that H2S-mediated Akt activation is a key step in protection against VILI, suggesting that Akt signaling limits not only inflammatory but also detrimental oxidative processes that promote the development of lung injury. PMID:28250891

  3. Macrophage uptake of low-density lipoprotein bound to aggregated C-reactive protein: possible mechanism of foam-cell formation in atherosclerotic lesions.

    PubMed Central

    Fu, Tao; Borensztajn, Jayme

    2002-01-01

    Foam cells found in atherosclerotic lesions are believed to derive from macrophages that take up aggregated low-density lipoprotein (LDL) particles bound to the extracellular matrix of arterial walls. C-reactive protein (CRP) is an acute-phase protein found in atherosclerotic lesions, which when immobilized on a solid phase, can bind and cluster LDL particles in a calcium-dependent manner. In the present study, we examined whether CRP-bound aggregated LDL could be taken up by macrophages in culture. CRP molecules were aggregated in the presence of calcium and immobilized on the surface of polystyrene microtitre wells. Human LDL added to the wells bound to and aggregated on the immobilized CRP, also in a calcium-dependent manner. On incubation with macrophages, the immobilized CRP-bound LDL aggregates were readily taken up by the cells, as demonstrated by immunofluorescence microscopy, by the cellular accumulation of cholesterol and by the overexpression of adipophilin. Immunofluorescence microscopy and flow-cytometry analysis established that the uptake of the LDL-CRP complex was not mediated by the CRP receptor CD32. These observations with immobilized CRP and LDL, approximating the conditions that exist in the extracellular matrix of the arterial wall, thus suggest that CRP may contribute to the formation of foam cells in atherosclerotic lesions by causing the aggregation of LDL molecules that are then taken up by macrophages through a CD32-independent pathway. PMID:12033985

  4. Iron-dependent formation of reactive oxygen species and glutathione depletion after accumulation of magnetic iron oxide nanoparticles by oligodendroglial cells

    NASA Astrophysics Data System (ADS)

    Hohnholt, Michaela C.; Dringen, Ralf

    2011-12-01

    Magnetic iron oxide nanoparticles (IONP) are currently used for various neurobiological applications. To investigate the consequences of a treatment of brain cells with such particles, we have applied dimercaptosuccinate (DMSA)-coated IONP that had an average hydrodynamic diameter of 60 nm to oligodendroglial OLN-93 cells. After exposure to 4 mM iron applied as DMSA-IONP, these cells increased their total specific iron content within 8 h 600-fold from 7 to 4,200 nmol/mg cellular protein. The strong iron accumulation was accompanied by a change in cell morphology, although the cell viability was not compromized. DMSA-IONP treatment caused a concentration-dependent increase in the iron-dependent formation of reactive oxygen species and a decrease in the specific content of the cellular antioxidative tripeptide glutathione. During a 16 h recovery phase in IONP-free culture medium following exposure to DMSA-IONP, OLN-93 cells maintained their high iron content and replenished their cellular glutathione content. These data demonstrate that viable OLN-93 cells have a remarkable potential to deal successfully with the consequences of an accumulation of large amounts of iron after exposure to DMSA-IONP.

  5. Fuel quality combustion analysis

    NASA Technical Reports Server (NTRS)

    Naegeli, D. W.; Moses, C. A.

    1979-01-01

    A high pressure research combustor operating over a wide range of burner inlet conditions was used to determine the effects of fuel molecular structure on soot formation. Six test fuels with equal hydrogen content (12.8%) were blended to stress different molecular components and final boiling points. The fuels containing high concentrations (20%) of polycyclic aromatics and partially saturated polycyclic structures such as tetralin, produced more soot than would be expected from a hydrogen content correlation for typical petroleum based fuels. Fuels containing naphthenes such as decalin agreed with the hydrogen content correlation. The contribution of polycyclic aromatics to soot formation was equivalent to a reduction in fuel hydrogen content of about one percent. The fuel sensitivity to soot formation due to the polycyclic aromatic contribution decreased as burner inlet pressure and fuel/air ratio increased.

  6. 13C Pathway Analysis for the Role of Formate in Electricity Generation by Shewanella Oneidensis MR-1 Using Lactate in Microbial Fuel Cells

    PubMed Central

    Luo, Shuai; Guo, Weihua; H. Nealson, Kenneth; Feng, Xueyang; He, Zhen

    2016-01-01

    Microbial fuel cell (MFC) is a promising technology for direct electricity generation from organics by microorganisms. The type of electron donors fed into MFCs affects the electrical performance, and mechanistic understanding of such effects is important to optimize the MFC performance. In this study, we used a model organism in MFCs, Shewanella oneidensis MR-1, and 13C pathway analysis to investigate the role of formate in electricity generation and the related microbial metabolism. Our results indicated a synergistic effect of formate and lactate on electricity generation, and extra formate addition on the original lactate resulted in more electrical output than using formate or lactate as a sole electron donor. Based on the 13C tracer analysis, we discovered decoupled cell growth and electricity generation in S. oneidensis MR-1 during co-utilization of lactate and formate (i.e., while the lactate was mainly metabolized to support the cell growth, the formate was oxidized to release electrons for higher electricity generation). To our best knowledge, this is the first time that 13C tracer analysis was applied to study microbial metabolism in MFCs and it was demonstrated to be a valuable tool to understand the metabolic pathways affected by electron donors in the selected electrochemically-active microorganisms. PMID:26868848

  7. ¹³C Pathway Analysis for the Role of Formate in Electricity Generation by Shewanella Oneidensis MR-1 Using Lactate in Microbial Fuel Cells.

    PubMed

    Luo, Shuai; Guo, Weihua; Nealson, Kenneth H; Feng, Xueyang; He, Zhen

    2016-02-12

    Microbial fuel cell (MFC) is a promising technology for direct electricity generation from organics by microorganisms. The type of electron donors fed into MFCs affects the electrical performance, and mechanistic understanding of such effects is important to optimize the MFC performance. In this study, we used a model organism in MFCs, Shewanella oneidensis MR-1, and (13)C pathway analysis to investigate the role of formate in electricity generation and the related microbial metabolism. Our results indicated a synergistic effect of formate and lactate on electricity generation, and extra formate addition on the original lactate resulted in more electrical output than using formate or lactate as a sole electron donor. Based on the (13)C tracer analysis, we discovered decoupled cell growth and electricity generation in S. oneidensis MR-1 during co-utilization of lactate and formate (i.e., while the lactate was mainly metabolized to support the cell growth, the formate was oxidized to release electrons for higher electricity generation). To our best knowledge, this is the first time that (13)C tracer analysis was applied to study microbial metabolism in MFCs and it was demonstrated to be a valuable tool to understand the metabolic pathways affected by electron donors in the selected electrochemically-active microorganisms.

  8. 13C Pathway Analysis for the Role of Formate in Electricity Generation by Shewanella Oneidensis MR-1 Using Lactate in Microbial Fuel Cells

    NASA Astrophysics Data System (ADS)

    Luo, Shuai; Guo, Weihua; H. Nealson, Kenneth; Feng, Xueyang; He, Zhen

    2016-02-01

    Microbial fuel cell (MFC) is a promising technology for direct electricity generation from organics by microorganisms. The type of electron donors fed into MFCs affects the electrical performance, and mechanistic understanding of such effects is important to optimize the MFC performance. In this study, we used a model organism in MFCs, Shewanella oneidensis MR-1, and 13C pathway analysis to investigate the role of formate in electricity generation and the related microbial metabolism. Our results indicated a synergistic effect of formate and lactate on electricity generation, and extra formate addition on the original lactate resulted in more electrical output than using formate or lactate as a sole electron donor. Based on the 13C tracer analysis, we discovered decoupled cell growth and electricity generation in S. oneidensis MR-1 during co-utilization of lactate and formate (i.e., while the lactate was mainly metabolized to support the cell growth, the formate was oxidized to release electrons for higher electricity generation). To our best knowledge, this is the first time that 13C tracer analysis was applied to study microbial metabolism in MFCs and it was demonstrated to be a valuable tool to understand the metabolic pathways affected by electron donors in the selected electrochemically-active microorganisms.

  9. Influence of the reactive atmosphere on the formation of nanoparticles in the plasma plume induced by nanosecond pulsed laser irradiation of metallic targets at atmospheric pressure and high repetition rate

    NASA Astrophysics Data System (ADS)

    Girault, M.; Le Garrec, J.-L.; Mitchell, J. B. A.; Jouvard, J.-M.; Carvou, E.; Menneveux, J.; Yu, J.; Ouf, F.-X.; Carles, S.; Potin, V.; Pillon, G.; Bourgeois, S.; Perez, J.; Marco de Lucas, M. C.; Lavisse, L.

    2016-06-01

    The influence of a reactive atmosphere on the formation of nanoparticles (NPs) in the plasma plume generated by nanosecond pulsed laser irradiation of metal targets (Ti, Al, Ag) was probed in situ using Small Angle X-ray Scattering (SAXS). Air and different O2-N2 gas mixtures were used as reactive gas within atmospheric pressure. SAXS results showed the formation of NPs in the plasma-plume with a mean radius varying in the 2-5 nm range. A decrease of the NPs size with increasing the O2 percentage in the O2-N2 gas mixture was also showed. Ex situ observations by transmission electron microscopy and structural characterizations by X-ray diffraction and Raman spectroscopy were also performed for powders collected in experiments done using air as ambient gas. The stability of the different metal oxides is discussed as being a key parameter influencing the formation of NPs in the plasma-plume.

  10. Analysis of the effect of transverse power distribution in an involute fuel plate with and without oxide film formation.

    SciTech Connect

    Smith, R. S.

    1998-10-27

    Existing thermal hydraulics computer codes can account for variations in power and temperature in the axial and thickness directions but variations across the width of the plate cannot be accounted for. In the case of fuel plates in an annular core this can lead to significant errors which are accentuated by the presence of an oxide layer that builds up on the aluminum cladding with burnup. This paper uses a three dimensional SINDA model to account for the transverse variations in power. The effect of oxide thickness on these differences is studied in detail. Power distribution and fuel conductivity are also considered. The lower temperatures predicted with the SINDA model result in a greater margin to clad and fuel damage.

  11. On the Experimental and Theoretical Investigations of Lean Partially Premixed Combustion, Burning Speed, Flame Instability and Plasma Formation of Alternative Fuels at High Temperatures and Pressures

    NASA Astrophysics Data System (ADS)

    Askari, Omid

    This dissertation investigates the combustion and injection fundamental characteristics of different alternative fuels both experimentally and theoretically. The subjects such as lean partially premixed combustion of methane/hydrogen/air/diluent, methane high pressure direct-injection, thermal plasma formation, thermodynamic properties of hydrocarbon/air mixtures at high temperatures, laminar flames and flame morphology of synthetic gas (syngas) and Gas-to-Liquid (GTL) fuels were extensively studied in this work. These subjects will be summarized in three following paragraphs. The fundamentals of spray and partially premixed combustion characteristics of directly injected methane in a constant volume combustion chamber have been experimentally studied. The injected fuel jet generates turbulence in the vessel and forms a turbulent heterogeneous fuel-air mixture in the vessel, similar to that in a Compressed Natural Gas (CNG) Direct-Injection (DI) engines. The effect of different characteristics parameters such as spark delay time, stratification ratio, turbulence intensity, fuel injection pressure, chamber pressure, chamber temperature, Exhaust Gas recirculation (EGR) addition, hydrogen addition and equivalence ratio on flame propagation and emission concentrations were analyzed. As a part of this work and for the purpose of control and calibration of high pressure injector, spray development and characteristics including spray tip penetration, spray cone angle and overall equivalence ratio were evaluated under a wide range of fuel injection pressures of 30 to 90 atm and different chamber pressures of 1 to 5 atm. Thermodynamic properties of hydrocarbon/air plasma mixtures at ultra-high temperatures must be precisely calculated due to important influence on the flame kernel formation and propagation in combusting flows and spark discharge applications. A new algorithm based on the statistical thermodynamics was developed to calculate the ultra-high temperature plasma

  12. The impact of steam and current density on carbon formation from biomass gasification tar on Ni/YSZ, and Ni/CGO solid oxide fuel cell anodes

    NASA Astrophysics Data System (ADS)

    Mermelstein, Joshua; Millan, Marcos; Brandon, Nigel

    The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports an experimental study on the mitigation of carbon formation arising from the exposure of the commonly used Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium-doped ceria) SOFC anodes to biomass gasification tars. Carbon formation and cell degradation was reduced through means of steam reforming of the tar over the nickel anode, and partial oxidation of benzene model tar via the transport of oxygen ions to the anode while operating the fuel cell under load. Thermodynamic calculations suggest that a threshold current density of 365 mA cm -2 was required to suppress carbon formation in dry conditions, which was consistent with the results of experiments conducted in this study. The importance of both anode microstructure and composition towards carbon deposition was seen in the comparison of Ni/YSZ and Ni/CGO anodes exposed to the biomass gasification tar. Under steam concentrations greater than the thermodynamic threshold for carbon deposition, Ni/YSZ anodes still exhibited cell degradation, as shown by increased polarization resistances, and carbon formation was seen using SEM imaging. Ni/CGO anodes were found to be more resilient to carbon formation than Ni/YSZ anodes, and displayed increased performance after each subsequent exposure to tar, likely due to continued reforming of condensed tar on the anode.

  13. Numerical simulation of air and oxy-fuel combustion of single coal particles using the reactive implicit continuous-fluid Eulerian (RICE) method

    NASA Astrophysics Data System (ADS)

    Lewtak, Robert

    2013-10-01

    The paper presents the mathematical model of air and oxy-fuel combustion of single coal particles. The combustion process has been treated as a spherically-symmetric one. The 1-dimensional time-dependent conservation equations governing the process have been numerically solved using the RICE method. The presence of a coal particle, which was treated as a discrete Lagrange particle, has modified the boundary conditions at the gas-solid interface. Numerical results show good agreement with the experimental results.

  14. Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation

    NASA Technical Reports Server (NTRS)

    Frenklach, M.

    1983-01-01

    Soot formation in toluene-, benzene-, and acetylene-oxygen-argon mixtures was investigated to study soot formation in a combustion environment. High concentrations of oxygen completely suppress soot formation. The addition of oxygen at relatively low concentrations uniformly suppresses soot formation at high pressures, while at relatively lower pressures it suppresses soot formation at higher temperatures while promoting soot production at lower temperatures. The observed behavior indicates that oxidation reactions compete with ring fragmentation. The main conclusion to be drawn from the results is that the soot formation mechanism is probably the same for the pyrolysis and oxidation of hydrocarbons. That is, the addition of oxygen does not alter the soot route but rather promotes or inhibits this route by means of competitive reactions. An approach to empirical modeling of soot formation during pyrolysis of aromatic hydrocarbons is also presented.

  15. Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

    PubMed

    Ravella, Uday K; Liu, Jingjing; Corbel, Gwenaël; Skinner, Stephen J; Lacorre, Philippe

    2016-08-23

    Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 μm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) .

  16. 08FFL-0020Influence of High Fuel Rail Pressure and Urea Selective Catalytic Reduction on PM Formation in an Off-Highway Heavy-Duty Diesel Engine

    SciTech Connect

    Kass, Michael D; Domingo, Norberto; Storey, John Morse; Lewis Sr, Samuel Arthur

    2008-01-01

    The influence of fuel rail pressure (FRP) and urea-selective catalytic reduction (SCR) on particulate matter (PM) formation is investigated in this paper along with notes regarding the NOx and other emissions. Increasing FRP was shown to reduce the overall soot and total PM mass for four operating conditions. These conditions included two high speed conditions (2400 rpm at 540 and 270 Nm of torque) and two moderated speed conditions (1400 rpm at 488 and 325 Nm). The concentrations of CO2 and NOx increased with fuel rail pressure and this is attributed to improved fuel-air mixing. Interestingly, the level of unburned hydrocarbons remained constant (or increased slightly) with increased FRP. PM concentration was measured using an AVL smoke meter and scanning mobility particle sizer (SMPS); and total PM was collected using standard gravimetric techniques. These results showed that the smoke number and particulate concentrations decrease with increasing FRP. However the decrease becomes more gradual as very high rail pressures. Additionally, the total PM decreased with increasing FRP; however, the soluble organic fraction (SOF) reaches a maximum after which it declines with higher rail pressure. The total PM was collected for the two 1400 rpm conditions downstream of the engine, diesel oxidation catalyst, and a urea-SCR catalyst. The results show that significant PM reduction occurs in the SCR catalyst even during high rates of urea dosage. Analysis of the PM indicates that residual SOF is burned up in the SCR catalyst.

  17. Reactive Gaseous Mercury Formation Over The North Pacific Ocean: Influence Of Environmental Parameters On Elemental Mercury Oxidation In The Marine Boundary Layer

    NASA Astrophysics Data System (ADS)

    Laurier, F. J.

    2002-12-01

    Global mercury models have identified wet and dry particle deposition and evasion of dissolved gaseous mercury from the ocean and from land as key controls over global mercury cycling (1,2). Recent ocean studies (3,4) however, have indicated that estimated mercury evasion rates from the ocean substantially exceed estimated deposition. Oxidized reactive gaseous mercury species (RGHg) are now known to play a major role in the global mercury cycle (2,5). RGHg species are water-soluble, exhibit a much shorter atmospheric lifetime than elemental mercury, and contribute to a large extent to atmospheric mercury deposition (2,3,6). Although recent global mercury models have accounted for the dry deposition of RGHg derived from point source emissions (6,7), the formation and deposition of RGHg in remote areas have not been incorporated. We suggest that the oxidation of elemental mercury over the ocean, by gas phase or heterogeneous reactions, is an important part the global mercury cycle. In agreement with previous studies (3,8,9) our recent data from atmospheric collections over the North Pacific Ocean support the notion of enhanced oxidation in the marine boundary layer. Our results show an inverse correlation between RGHg production and ozone, and a diurnal cycle with highest concentrations during periods of highest UV irradiation. In addition, the relationship between RGHg and other parameters measured during the cruise will be discussed. Our results clearly show that RGHg deposition to the ocean must be an important Hg source, and a crucial part of the global Hg cycle. (1) Mason R.P., Fitzgerald W.F., and Morel F.M.M. (1994), The biogeochemical cycling of elemental mercury: Anthropogenic influences, Geochim. Cosmochim. Acta, 58: 3191-3198 (2) Shia R.L., Seigneur C., Pai P., Ko M., and Sze N.-D. (1999), Global simulation of atmospheric mercury concentrations and deposition fluxes, J. Geophy. Res., 104(D19), 23, 747-23, 760 (3) Mason, R.P., Lawson N.M., and Sheu G

  18. A role of hydrocarbon reaction for NO{sub x} formation and reduction in fuel-rich pulverized coal combustion

    SciTech Connect

    Taniguchi, Masayuki; Kamikawa, Yuki; Okazaki, Teruyuki; Yamamoto, Kenji; Orita, Hisayuki

    2010-08-15

    We have investigated an index for modeling a NO{sub x} reaction mechanism of pulverized coal combustion. The reaction mechanism of coal nitrogen was examined by drop-tube furnace experiments under various burning conditions. We proposed the gas phase stoichiometric ratio (SRgas) as a key index to evaluate NO{sub x} concentration in fuel-rich flames. The SRgas was defined as: SRgas {identical_to} amount of fuel required for stoichiometry combustion/amount of gasified fuel where, the amount of gasified fuel was defined as the amount of fuel which had been released to the gas phase by pyrolysis, oxidation and gasification reactions. When SRgas < 1.0, NO{sub x} concentration was strongly influenced by the value of SRgas. In this condition, the NO{sub x} concentration was hardly influenced by coal type, particle diameter, or reaction time. We developed a model to analyze NO{sub x} and XN(HCN, NH{sub 3}) concentrations for pulverized coal/air combustion and coal/CO{sub 2}/O{sub 2} combustion, based on the index. NO{sub x} and XN concentrations did not reproduce the experimental results without considering reactions between hydrocarbons and NO{sub x}. The hydrocarbon reaction was important for both NO{sub x} and XN, especially for air combustion. In the present model, an empirical formula was used to estimate the total concentration of hydrocarbons in coal flame. The reaction of heavy hydrocarbons which had plural aromatic rings was very important to analyze the reaction mechanism of hydrocarbons for coal combustion in detail. When burning temperature and SRgas were the same, total hydrocarbon concentration in a coal flame was larger than that of a light gaseous hydrocarbon flame. Total hydrocarbon concentration in oxy-fuel combustion was lower than that in air combustion. We verified the proposed model by experimental results obtained for a drop-tube furnace and a laboratory-scale furnace that had an installed low-NO{sub x} burner. (author)

  19. Chemical Characterization and Formation of Reactive Oxygen Species by PM2.5 during Summer in North China Plain of China

    NASA Astrophysics Data System (ADS)

    Zheng, M.; Li, X.; Kuang, X.; Yan, C.; Guo, X.; Paulson, S. E.

    2015-12-01

    Ambient particulate matter (PM) could cause adverse health effects by generating reactive oxygen species (ROS) including superoxide (·O2-), hydrogen peroxide (HOOH), and hydroxyl radical (·OH). A number of studies have shown that transition metals, quinones, as well as other unknown organics in particles, may contribute to ROS formation. North China Plain (NCP) is one of the most populated and polluted areas in the world, where Beijing, the capital of China, is located. NCP have been suffering from severe air pollution, and health effects of fine PM have drawn great attentions of both the government and the public. To study the chemical characterization and ROS generation of PM, airborne PM2.5 was collected at two sites, with one urban site on the campus of Peking University in Beijing and one suburban site in Wangdu, Hebei Province, which is located in the south of Beijing and was significantly influenced by biomass burning during the study period. Previous studies have shown that Beijing can be more influenced by regional transport when the prevailing wind is from the south. PM2.5 samples were collected on 47 mm Teflon filter and Quartz filter using the four-channel low-volume sampler, and organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), soluble ions and trace metals have been analyzed. The formation of ·OH induced by PM2.5 was also measured to characterize the chemical generation of ROS from ambient particles in a cell-free solution. Preliminary analysis showed that during biomass burning periods, OC and EC concentrations in Wangdu were significantly higher than that in Beijing. The average concentration of WSOC in Beijing was comparable to that in Wangdu, while during biomass burning period, that in Wangdu was much higher than that in Beijing. Positive matrix factorization (PMF) was applied to identify the major contributing sources of PM2.5. More detailed information about chemical compositions, sources and ROS generation of

  20. Formation of a unique zinc carbamate by CO2 fixation: implications for the reactivity of tetra-azamacrocycle ligated Zn(II) complexes.

    PubMed

    Notni, Johannes; Schenk, Stephan; Görls, Helmar; Breitzke, Hergen; Anders, Ernst

    2008-02-18

    The macrocyclic ligand [13]aneN 4 ( L1, 1,4,7,10-tetra-azacyclotridecane) was reacted with Zn(II) perchlorate and CO 2 in an alkaline methanol solution. It was found that, by means of subtle changes in reaction conditions, two types of complexes can be obtained: (a) the mu 3 carbonate complex 1, {[Zn( L1)] 3(mu 3-CO 3)}(ClO 4) 4, rhombohedral crystals, space group R3 c, with pentacoordinate zinc in a trigonal bipyramidal enviroment, and (b) an unprecedenced dimeric Zn(II) carbamate structure, 2, [Zn( L2)] 2(ClO 4) 2, monoclinic crystals, space group P2 1/ n. The ligand L2 (4-carboxyl-1,4,7,10-tetra-azacyclotridecane) is a carbamate derivative of L1, obtained by transformation of a hydrogen atom of one of the NH moieties into carbamate by means of CO 2 uptake. In compound 2, the distorted tetrahedral Zn(II) coordinates to the carbamate moiety in a monodentate manner. Most notably, carbamate formation can occur upon reaction of CO 2 with the [Zn L1] (2+) complex, which implicates that a Zn-N linkage is cleaved upon attack of CO 2. Since complexes of tetra-azamacrocycles and Zn(II) are routinely applied for enzyme model studies, this finding implies that the Zn-azamacrocycle moiety generally should no longer be considered to play always only an innocent role in reactions. Rather, its reactivity has to be taken into account in respective investigations. In the presence of water, 2 is transformed readily into carbonate 1. Both compounds have been additionally characterized by solid-state NMR and infrared spectroscopy. A thorough comparison of 1 with related azamacrocycle ligated zinc(II) carbonates as well as a discussion of plausible reaction paths for the formation of 2 are given. Furthermore, the infrared absorptions of the carbamate moiety have been assigned by calculating the vibrational modes of the carbamate complex using DFT methods and the vibrational spectroscopy calculation program package SNF.

  1. mGluR5 stimulating Homer–PIKE formation initiates icariin induced cardiomyogenesis of mouse embryonic stem cells by activating reactive oxygen species

    SciTech Connect

    Zhou, Limin; Huang, Yujie; Zhang, Yingying; Zhao, Qingwei; Zheng, Bei; Lou, Yijia; Zhu, Danyan

    2013-06-10

    Icariin (ICA) has been reported to facilitate cardiac differentiation of mouse embryonic stem (ES) cells; however, the mechanism by which ICA induced cardiomyogenesis has not been fully elucidated yet. Here, an underlying signaling network including metabotropic glutamate receptor 5 (mGluR5), Homer, phosphatidylinositol 3-Kinase Enhancer (PIKE), phosphatidylinositol 3-Kinase (PI3K), reactive oxygen species (ROS) and nuclear factor-kappaB (NF-κB) was investigated in ICA induced cardiomyogenesis. Our results showed that the co-expression of mGluR5 together with α-actinin or Troponin T in embryoid bodies (EBs) treated with ICA was elevated to 10.86% and 9.62%, compared with the case in the control (4.04% and 3.45%, respectively). Exposure of EBs to ICA for 2 h remarkably increased the dimeric form of mGluR5, which was inhibited by small interfering RNA targeting mGluR5 (si-mGluR5). Moreover, the extracellular glutamate concentration in ICA treatment medium was elevated to 28.9±3.5 μM. Furthermore, the activation of mGluR5 by ICA triggered the formation of Homer–PIKE complex and activated PI3K, stimulating ROS generation and NF-κB nuclear translocation. Knockdown of mGluR5 or inhibition of PI3K by LY294002 blocked ICA induced cardiomyogenesis via repressing mGluR5 pathway, reducing ROS and NF-κB activation. These results revealed that the inducible mechanisms of ICA were related to activate mGluR5 pathway. -- Highlights: • ICA increased mGluR5 expression in cardiac differentiation of ES cells. • ICA enhanced the glutamate level and the receptor mGluR5 dimerization, stimulating the formation of Homer–PIKE complex. • Knockdown of mGluR5 or inhibition of PI3K by LY294002 inhibited ICA induced ROS generation and NF-κB nuclear translocation.

  2. High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

    NASA Astrophysics Data System (ADS)

    Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

    2016-05-01

    We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

  3. High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

    PubMed Central

    Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

    2016-01-01

    We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

  4. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion.

    PubMed

    Sasikumar, Swamiappan; Vijayaraghavan, Rajagopalan

    2008-07-01

    Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4)6 (OH)2) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye-Scherrer formula, is in the range 20-30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  5. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    PubMed Central

    Sasikumar, Swamiappan; Vijayaraghavan, Rajagopalan

    2008-01-01

    Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4)6 (OH)2) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66. PMID:27878000

  6. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    NASA Astrophysics Data System (ADS)

    Sasikumar, Swamiappan; Vijayaraghavan, Rajagopalan

    2008-07-01

    Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4)6 (OH)2) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye-Scherrer formula, is in the range 20-30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  7. Study of scale formation on AISI 316L in simulated solid oxide fuel cell bi-polar environments

    SciTech Connect

    Ziomek-Moroz, M.; Covino, Bernard S., Jr.; Cramer, Stephen D.; Holcomb, Gordon R.; Bullard, Sophie J.; Singh , P.; Windisch, C.F., Jr.

    2004-01-01

    Significant progress made towards reducing the operating temperature of solid oxide fuel cells (SOFC) from {approx}1000 C to {approx}600 C is expected to permit the use of metallic materials with substantial cost reduction. One of the components in a SOFC stack to be made of metallic materials is a bipolar separator, also called an interconnect. It provides electrical connection between individual cells and serves as a gas separator to prevent mixing of the fuel and air. At operating temperature, the material selected for interconnects should possess good chemical and mechanical stability in complex fuel and oxidant gaseous environments, good electrical conductivity, and a coefficient of thermal expansion (CTE) that matches that of the cathode, anode, and electrolyte components. Cr2O3 scale-forming alloys appear to be the most promising candidates. There appears to be a mechanism whereby the environment on the fuel side of a stainless steel interconnect changes the corrosion behavior of the metal on the air side. The corrosion behavior of 316L stainless steel simultaneously exposed to air on one side and H2+3%H2O on the other at 907 K was studied using X-ray diffraction (XRD) and Raman spectroscopy. The electrical property of the investigated material was determined in terms of area-specific resistance (ASR). The chemical and electrical properties of 316L exposed to a dual environment of air/ (H2+H2O) were compared to those of 316L exposed to a single environment of air/air.

  8. Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells

    PubMed Central

    Show, Yoshiyuki; Ueno, Yutaro

    2017-01-01

    Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2. PMID:28336864

  9. Reactivity measurements on an experimental assembly of 4. 31 wt % sup 235 U enriched UO sub 2 fuel rods arranged in a shipping cask geometry

    SciTech Connect

    Bierman, S.R.

    1989-10-01

    A research program was initiated for the US Department of Energy (DOE) Sandia National Laboratory Transportation Systems Development Department in 1982 to provide benchmark type experimental criticality data in support of the design and safe operations of nuclear fuel transportation systems. The overall objective of the program is to identify and provide the experimental data needed to form a consistent, firm, and complete data base for verifying calculational models used in the criticality analyses of nuclear transport and related systems. A report, PNL-6205, issued in June 1988 (Bierman 1988) covered measurement results obtained from a series of experimental assemblies (TIC-1, 2, 3 and 4) involving neutron flux traps. The results obtained on a fifth experimental assembly (TIC-5), modeled after a calculational problem of the Organization for Economic Cooperation and Development (OECD) Nuclear Energy Agency (NEA) Committee on the Safety of Nuclear Installations (CSNI) Working Group, are covered in this report. 10 refs., 10 figs., 7 tabs.

  10. Thermal breeder fuel enrichment zoning

    DOEpatents

    Capossela, Harry J.; Dwyer, Joseph R.; Luce, Robert G.; McCoy, Daniel F.; Merriman, Floyd C.

    1992-01-01

    A method and apparatus for improving the performance of a thermal breeder reactor having regions of higher than average moderator concentration are disclosed. The fuel modules of the reactor core contain at least two different types of fuel elements, a high enrichment fuel element and a low enrichment fuel element. The two types of fuel elements are arranged in the fuel module with the low enrichment fuel elements located between the high moderator regions and the high enrichment fuel elements. Preferably, shim rods made of a fertile material are provided in selective regions for controlling the reactivity of the reactor by movement of the shim rods into and out of the reactor core. The moderation of neutrons adjacent the high enrichment fuel elements is preferably minimized as by reducing the spacing of the high enrichment fuel elements and/or using a moderator having a reduced moderating effect.

  11. The formation of Ca-Cl-rich groundwaters in the Dry Valleys of Antarctica: Field measurements and modeling of reactive transport

    NASA Astrophysics Data System (ADS)

    Toner, Jonathan D.; Sletten, Ronald S.

    2013-06-01

    Ca-Cl-rich brines have been found in shallow subsurface flows, groundwater systems, lakes, and ponds throughout the Dry Valleys of Antarctica. The apparent abundance of Ca-Cl-rich waters near the surface is unusual compared to global surface water compositions and a number of theories have been proposed to explain the genesis of these brines. We show that an ice-cemented soil developing on fluvial sediment in Taylor Valley also contains Ca-Cl-rich brine. The distribution of soluble ions, exchangeable cations, and stable isotopes down to 2.1 m depth in the soil suggests that CaCl2 was formed by cation exchange reactions during downward reactive transport of Na-Cl-rich brine from the soil surface. To explore the implications of exchange reactions for the formation of Ca-Cl-rich brine, Ca-Na and Ca-Mg exchange properties were measured in 1 mM, 0.1 M, and 4.75 M solutions. Low-temperature reactions and brine transport were modeled in PHREEQC by incorporating FREZCHEM Pitzer parameters and solubility products into PHREEQC. Modeling shows that by freezing soils in equilibrium with Dry Valley surface waters, a strong Ca-Mg enrichment of the soil solution is caused by the exchange of aqueous Na+ with exchangeable Ca2+ and Mg2+. Ca-Mg enrichment also occurs as Na-Cl-rich brine from the soil surface advects into ice-cemented soil. By modeling this process in the borehole soil, trends in ion distributions with depth can be predicted. Brine compositions from cation exchange reactions are consistent with Ca-Cl-rich brine compositions in the Dry Valleys, although additional water-rock interaction is proposed to account for the low Mg2+ concentrations in Don Juan Pond. Furthermore, the amount of CaCl2 that can be produced by exchange reactions is consistent with estimated amounts of CaCl2 in groundwaters beneath Don Juan Pond. This suggests that cation exchange reactions can explain the Ca-Cl-rich composition of the enigmatic Don Juan Pond and other brines in the Dry Valleys.

  12. The problems of mass transfer and formation of deposits of corrosion products on fuel assemblies of a VVER-1200 reactor

    NASA Astrophysics Data System (ADS)

    Rodionov, Yu. A.; Kritskii, V. G.; Berezina, I. G.; Gavrilov, A. V.

    2014-03-01

    On the basis of examination of materials published both in Russia and abroad, as well as their own investigations, the authors explain the reasons for the occurrence of such effects as AOA (Axial Offset Anomalies) and an increase in the coolant pressure difference in the core of nuclear reactors of the VVER type. To detect the occurrence of the AOA effect, the authors suggest using the specific activity of 58Co in the coolant. In the VVER-1200 design the thermohydraulic regime for fuel assemblies in the first year of their service life involves slight boiling of the coolant in the upper part of the core, which may induce the occurrence of the AOA effect, intensification of corrosion of fuel claddings, and abnormal increase in deposition of corrosion products. Radiolysis of the water coolant in the boiling section (boiling in pores of deposits) may intensify not only general corrosion but also a localized (nodular) one. As a result of intensification of the corrosion processes and growth of deposits, deterioration of the radiation situation in the rooms of the primary circuit of a VVER-1200 reactor as compared to that at nuclear power plants equipped with reactors of the VVER-1000 type is possible. Recommendations for preventing the AOA effect at nuclear power plants with VVER-1200 reactors on the matter of the direction of further investigations are made.

  13. Studies on phase formation, microstructure development and elastic properties of reduced NiO-8YSZ anode supported bi-layer half-cell structures of solid oxide fuel cells

    SciTech Connect

    Nithyanantham, T.; Biswas, S.; Thangavel, S.N.; Bandopadhyay, S.

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Detailed study on the development of microstructure and phase in NiO-8YSZ anodes. Black-Right-Pointing-Pointer Detailed study on elastic properties at high temperatures in air/reducing atmosphere. Black-Right-Pointing-Pointer Effects of initial porosity, composition and other issues are evaluated in detail. -- Abstract: Half-cell structures of solid oxide fuel cells (SOFCs) with a thin and dense electrolyte layer of 8YSZ supported by a thick and porous NiO-8YSZ anode precursor structure were reduced in a gas mixture of 5% H{sub 2}-95% Ar at 800 Degree-Sign C for selected time periods in order to fabricate cermets with desired microstructure and composition, and to study their effects on the elastic properties at ambient and reactive atmospheres. It appears that 2 h of exposure to the reducing conditions is enough to reduce {approx}80% of NiO with an enhanced porosity value of 35%. The Ni-8YSZ cermet phase formation in the anode was analyzed with X-ray diffraction (XRD) in correlation with its microstructure. The elastic properties were determined after the reduction, at room and elevated temperatures using the impulse excitation technique. At room temperature the decrease in the Young's modulus was about 44% (after 8 h of reduction) and can be attributed mainly to the changes in the microstructure, particularly the increase in porosity from {approx}12% to 37%. Young's moduli of the as-received precursor and reduced anodes were evaluated as a function of temperature in air and reducing atmosphere. The results were explained in correlation to the initial porosity, composition and oxidation of Ni at the elevated temperatures.

  14. Fuel cells and fuel cell catalysts

    DOEpatents

    Masel, Richard I.; Rice, Cynthia A.; Waszczuk, Piotr; Wieckowski, Andrzej

    2006-11-07

    A direct organic fuel cell includes a formic acid fuel solution having between about 10% and about 95% formic acid. The formic acid is oxidized at an anode. The anode may include a Pt/Pd catalyst that promotes the direct oxidation of the formic acid via a direct reaction path that does not include formation of a CO intermediate.

  15. Multi-functional reactively-sputtered copper oxide electrodes for supercapacitor and electro-catalyst in direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Pawar, Sambhaji M.; Kim, Jongmin; Inamdar, Akbar I.; Woo, Hyeonseok; Jo, Yongcheol; Pawar, Bharati S.; Cho, Sangeun; Kim, Hyungsang; Im, Hyunsik

    2016-02-01

    This work reports on the concurrent electrochemical energy storage and conversion characteristics of granular copper oxide electrode films prepared using reactive radio-frequency magnetron sputtering at room temperature under different oxygen environments. The obtained films are characterized in terms of their structural, morphological, and compositional properties. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscope studies reveal that granular, single-phase Cu2O and CuO can be obtained by controlling the oxygen flow rate. The electrochemical energy storage properties of the films are investigated by carrying out cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy tests. The electrochemical analysis reveals that the Cu2O and CuO electrodes have high specific capacitances of 215 and 272 F/g in 6 M KOH solution with a capacity retention of about 80% and 85% after 3000 cycles, respectively. Cyclic voltammetry and chronoamperometry are used to study the electrochemical energy conversion properties of the films via methanol electro-oxidation. The results show that the Cu2O and CuO electrodes are electro-catalytically active and highly stable.

  16. Multi-functional reactively-sputtered copper oxide electrodes for supercapacitor and electro-catalyst in direct methanol fuel cell applications

    PubMed Central

    Pawar, Sambhaji M.; Kim, Jongmin; Inamdar, Akbar I.; Woo, Hyeonseok; Jo, Yongcheol; Pawar, Bharati S.; Cho, Sangeun; Kim, Hyungsang; Im, Hyunsik

    2016-01-01

    This work reports on the concurrent electrochemical energy storage and conversion characteristics of granular copper oxide electrode films prepared using reactive radio-frequency magnetron sputtering at room temperature under different oxygen environments. The obtained films are characterized in terms of their structural, morphological, and compositional properties. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscope studies reveal that granular, single-phase Cu2O and CuO can be obtained by controlling the oxygen flow rate. The electrochemical energy storage properties of the films are investigated by carrying out cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy tests. The electrochemical analysis reveals that the Cu2O and CuO electrodes have high specific capacitances of 215 and 272 F/g in 6 M KOH solution with a capacity retention of about 80% and 85% after 3000 cycles, respectively. Cyclic voltammetry and chronoamperometry are used to study the electrochemical energy conversion properties of the films via methanol electro-oxidation. The results show that the Cu2O and CuO electrodes are electro-catalytically active and highly stable. PMID:26888077

  17. Pollutant formation in fuel lean recirculating flows. Ph.D. Thesis. Final Report; [in an Opposed Reacting Jet Combustor

    NASA Technical Reports Server (NTRS)

    Schefer, R. W.; Sawyer, R. F.

    1976-01-01

    An opposed reacting jet combustor (ORJ) was tested at a pressure of 1 atmosphere. A premixed propane/air stream was stabilized by a counterflowing jet of the same reactants. The resulting intensely mixed zone of partially reacted combustion products produced stable combustion at equivalence ratios as low as 0.45. Measurements are presented for main stream velocities of 7.74 and 13.6 m/sec with an opposed jet velocity of 96 m/sec, inlet air temperatures from 300 to 600 K, and equivalence ratios from 0.45 to 0.625. Fuel lean premixed combustion was an effective method of achieving low NOx emissions and high combustion efficiencies simultaneously. Under conditions promoting lower flame temperature, NO2 constituted up to 100 percent of the total NOx. At higher temperatures this percentage decreased to a minimum of 50 percent.

  18. Formation and High Reactivity of the anti-Dioxo Form of High-Spin μ-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C-H Bonds.

    PubMed

    Kodera, Masahito; Ishiga, Shin; Tsuji, Tomokazu; Sakurai, Katsutoshi; Hitomi, Yutaka; Shiota, Yoshihito; Sajith, P K; Yoshizawa, Kazunari; Mieda, Kaoru; Ogura, Takashi

    2016-04-18

    Recently, it was shown that μ-oxo-μ-peroxodiiron(III) is converted to high-spin μ-oxodioxodiiron(IV) through O-O bond scission. Herein, the formation and high reactivity of the anti-dioxo form of high-spin μ-oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic-absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ-oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluenereactive in the C-H bond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE for the reaction with toluene/[D8 ]toluene is 95 at -30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H2 O2 .

  19. Nondestrucive analysis of fuel pins

    DOEpatents

    Stepan, I.E.; Allard, N.P.; Suter, C.R.

    1972-11-03

    Disclosure is made of a method and a correspondingly adapted facility for the nondestructive analysis of the concentation of fuel and poison in a nuclear reactor fuel pin. The concentrations of fuel and poison in successive sections along the entire length of the fuel pin are determined by measuring the reactivity of a thermal reactor as each successive small section of the fuel pin is exposed to the neutron flux of the reactor core and comparing the measured reactivity with the reactivities measured for standard fuel pins having various known concentrations. Only a small section of the length of the fuel pin is exposed to the neutron flux at any one time while the remainder of the fuel pin is shielded from the neutron flux. In order to expose only a small section at any one time, a boron-10-lined dry traverse tube is passed through the test region within the core of a low-power thermal nuclear reactor which has a very high fuel sensitivity. A narrow window in the boron-10 lining is positioned at the core center line. The fuel pins are then systematically traversed through the tube past the narrow window such that successive small sections along the length of the fuel pin are exposed to the neutron flux which passes through the narrow window.

  20. Polarized advanced fuel reactors

    SciTech Connect

    Kulsrud, R.M.

    1987-07-01

    The d-/sup 3/He reaction has the same spin dependence as the d-t reaction. It produces no neutrons, so that if the d-d reactivity could be reduced, it would lead to a neutron-lean reactor. The current understanding of the possible suppression of the d-d reactivity by spin polarization is discussed. The question as to whether a suppression is possible is still unresolved. Other advanced fuel reactions are briefly discussed. 11 refs.

  1. Worksite translation of the Diabetes Prevention Program: formative research and pilot study results from FUEL Your Life.

    PubMed

    DeJoy, David M; Padilla, Heather M; Wilson, Mark G; Vandenberg, Robert J; Davis, Marsha A

    2013-07-01

    This article summarizes formative research and pilot study findings from a workplace translation of the Diabetes Prevention Program (DPP). The overarching goal was to devise a relatively straightforward weight management intervention suitable for use in a wide array of work settings. This project was conducted in conjunction with Union Pacific Railroad at one of their locomotive maintenance facilities. Participating employees were predominately male and middle-aged. Formative data were collected through stakeholder interviews, focus groups, and direct observation of the work environment. These results were used to adapt the DPP into a largely self-directed intervention augmented by peer health coaches and the on-site nurse. A small pilot test of the adapted program (n = 67) produced modest but statistically significant weight reductions at both 6 (core intervention period) and 12 months (maintenance period). These results are discussed in terms of the original DPP and other DPP translation studies.

  2. Formation and physical properties of uranium hydride under conditions relevant to metallic fuel and nuclear waste storage

    NASA Astrophysics Data System (ADS)

    Orr, Robin; Godfrey, Hugh; Broan, Chris; Goddard, Dave; Woodhouse, Guy; Durham, Peter; Diggle, Andrew; Bradshaw, John

    2016-08-01

    The formation of uranium hydride is recognised as a hazard during the storage of uranium metal owing to its potentially pyrophoric properties. This study has assessed the influence of water vapour on the potential for uranium hydride to form at low temperatures and shows that it increases the duration of the induction period but does not necessarily prevent uranium hydride formation and also does not significantly change the reaction rate with hydrogen. It is further shown that the α-UH3 fraction in the uranium hydride gradually increases at decreasing temperatures and is likely to be the dominant phase formed under typical storage conditions. Particle morphology and specific surface area of uranium hydride prepared between 30 °C and 200 °C have also been characterised but show only modest variation compared with the phase composition.

  3. Alternative aviation turbine fuels

    NASA Technical Reports Server (NTRS)

    Grobman, J.

    1977-01-01

    The efficient utilization of fossil fuels by future jet aircraft may necessitate the broadening of current aviation turbine fuel specifications. The most significant changes in specifications would be an increased aromatics content and a higher final boiling point in order to minimize refinery energy consumption and costs. These changes would increase the freezing point and might lower the thermal stability of the fuel and could cause increased pollutant emissions, increased smoke and carbon formation, increased combustor liner temperatures, and poorer ignition characteristics. This paper discusses the effects that broadened specification fuels may have on present-day jet aircraft and engine components and the technology required to use fuels with broadened specifications.

  4. PROBING REACTIVITY OF DISSOLVED ORGANIC MATTER FOR DISINFECTION BY-PRODUCT FORMATION USING XAD-8 RESIN ADSORPTION AND ULTRAFILTRATION FRACTIONATION. (R828045)

    EPA Science Inventory

    The disinfection by-product (DBP) reactivity (yield and speciation upon reaction with chlorine) of dissolved organic matter (DOM) isolated from two surface waters was investigated. The source waters, each having significantly different specific ultraviolet absorbance (SUVA

  5. Steric and electronic control over the reactivity of a thiolate-ligated Fe(II) complex with dioxygen and superoxide: reversible mu-oxo dimer formation.

    PubMed

    Theisen, Roslyn M; Shearer, Jason; Kaminsky, Werner; Kovacs, Julie A

    2004-11-29

    The reactivity between a thiolate-ligated five-coordinate complex [FeII(SMe2N4(tren))]+ (1) and dioxygen is examined in order to determine if O2 activation, resembling that of the metalloenzyme cytochrome P450, can be promoted even when O2 binds cis, as opposed to trans, to a thiolate. Previous work in our group showed that [FeII(SMe2N4(tren))]+ (1) reacts readily with superoxide (O2-) in the presence of a proton source to afford H2O2 via an Fe(III)-OOH intermediate, thus providing a biomimetic model for the metalloenzyme superoxide reductase (SOR). Addition of O2 to 1 affords binuclear mu-oxo-bridged [FeIII(SMe2N4(tren))]2(mu2-O)(PF6)2.3MeCN (3). At low temperatures, in protic solvents, an intermediate is detected, the details of which will be the subject of a separate paper. Although the thiolate ligand does not appear to perturb the metrical parameters of the unsupported mu-oxo bridge (Fe-O= 1.807(8) A, and Fe-O-Fe= 155.3(5) degrees fall in the usual range), it decreases the magnetic coupling between the irons (J=-28 cm(-1)) and creates a rather basic oxo site. Protonation of this oxo using strong (HBF4, HCl) or weak (HOAc, NH4PF6, LutNHCl) acids results in bridge cleavage to cleanly afford the corresponding monomeric anion-ligated (OAc- (6), or Cl- (7)) or solvent-ligated (MeCN (4)) derivatives. Addition of OH- converts [FeIII(SMe2N4(tren))(MeCN2+ (4) back to mu-oxo 3. Thus, mu-oxo bridge cleavage is reversible. The protonated mu-hydroxo-bridged intermediate is not observed. In an attempt to prevent mu-oxo dimer formation, and facilitate the observation of O2-bound intermediates, a bulkier tertiary amine ligand, tren-Et4= N-(2-amino-ethyl)-N-(2-diethylamino-ethyl)-N',N'-diethyl-ethane-1,2-diamine, and the corresponding [FeII(SMe2N4(tren-Et4))]+ (5) complex was synthesized and structurally characterized. Steric repulsive interactions create unusually long FeII-N(3,4) amine bonds in 5 (mean distance=2.219(1) A). The [(tren-Et4)N4SMe2]1- ligand is unable to

  6. Reactivity and Chemoselectivity of Allenes in Rh(I)-Catalyzed Intermolecular (5 + 2) Cycloadditions with Vinylcyclopropanes: Allene-Mediated Rhodacycle Formation Can Poison Rh(I)-Catalyzed Cycloadditions

    PubMed Central

    2015-01-01

    Allenes are important 2π building blocks in organic synthesis and engage as 2-carbon components in many metal-catalyzed reactions. Wender and co-workers discovered that methyl substituents on the terminal allene double bond counterintuitively change the reactivities of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with vinylcyclopropanes (VCPs). More sterically encumbered allenes afford higher cycloadduct yields, and such effects are also observed in other Rh(I)-catalyzed intermolecular cycloadditions. Through density functional theory calculations (B3LYP and M06) and experiment, we explored this enigmatic reactivity and selectivity of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with VCPs. The apparent low reactivity of terminally unsubstituted allenes is associated with a competing allene dimerization that irreversibly sequesters rhodium. With terminally substituted allenes, steric repulsion between the terminal substituents significantly increases the barrier of allene dimerization while the barrier of the (5 + 2) cycloaddition is not affected, and thus the cycloaddition prevails. Computation has also revealed the origin of chemoselectivity in (5 + 2) cycloadditions with allene-ynes. Although simple allene and acetylene have similar reaction barriers, intermolecular (5 + 2) cycloadditions of allene-ynes occur exclusively at the terminal allene double bond. The terminal double bond is more reactive due to the enhanced d−π* backdonation. At the same time, insertion of the internal double bond of an allene-yne has a higher barrier as it would break π conjugation. Substituted alkynes are more difficult to insert compared with acetylene, because of the steric repulsion from the additional substituents. This leads to the greater reactivity of the allene double bond relative to the alkynyl group in allene-ynes. PMID:25379606

  7. Controls on reflux dolomitisation of epeiric-scale ramps: Insights from reactive transport simulations of the Mississippian Madison Formation (Montana and Wyoming)

    NASA Astrophysics Data System (ADS)

    Gabellone, Tatyana; Whitaker, Fiona; Katz, David; Griffiths, Graham; Sonnenfeld, Mark

    2016-11-01

    Prediction of the geometry and petrophysical properties of dolomite geobodies depends on understanding both the hydrological system supplying reactive fluids and the chemistry of these fluids. However, patterns are complicated by the non-linear response of the diagenetic system to depositional texture, which controls both fluid flux via permeability architecture and reaction rate via effective surface area. This study explores interactions between extrinsic controls (spatial distribution of brine composition and temperature) and intrinsic controls (permeability and reactivity) using local and regional scale reactive transport models of sequential episodes of brine reflux that resulted in partial dolomitisation of the Mississippian Madison ramp. Inter-well scale models show preferential early dolomitisation of fine grained, more reactive beds. Pervasive dolomitisation can occur most readily beneath the brine pool where flow is perpendicular to bedding, and is most rapid at high brine fluxes. Down-dip of the brine pool, bedding-parallel flow is focused in relatively permeable coarse grained beds, providing reactants for strongly preferential alteration of intervening more reactive fine grained beds. In contrast, thicker sequences of fine grained beds dolomitise more slowly, limited by the rate of supply of magnesium. Regional-scale models, with injection of brines of increasing salinity towards the ramp interior, reproduce the observed pattern of dolomitisation. However, more realistic simulations in which reflux is driven by lateral density contrasts, generate flow rates orders of magnitude too low for significant dolomitisation. Simulations suggest pervasive dolomitisation of epeiric-scale ramps by a platform-wide reflux circulation, as often invoked, is not feasible. Rather, dolomitisation of such extensive systems critically requires local-scale flow systems, such as may result from topographically-controlled variations in restriction of platform-top seawater

  8. Low contaminant formic acid fuel for direct liquid fuel cell

    DOEpatents

    Masel, Richard I.; Zhu, Yimin; Kahn, Zakia; Man, Malcolm

    2009-11-17

    A low contaminant formic acid fuel is especially suited toward use in a direct organic liquid fuel cell. A fuel of the invention provides high power output that is maintained for a substantial time and the fuel is substantially non-flammable. Specific contaminants and contaminant levels have been identified as being deleterious to the performance of a formic acid fuel in a fuel cell, and embodiments of the invention provide low contaminant fuels that have improved performance compared to known commercial bulk grade and commercial purified grade formic acid fuels. Preferred embodiment fuels (and fuel cells containing such fuels) including low levels of a combination of key contaminants, including acetic acid, methyl formate, and methanol.

  9. Ab initio study of vacancy formation in cubic LaMnO3 and SmCoO3 as cathode materials in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Olsson, Emilia; Aparicio-Anglès, Xavier; de Leeuw, Nora H.

    2016-07-01

    Doped LaMnO3 and SmCoO3 are important solid oxide fuel cell cathode materials. The main difference between these two perovskites is that SmCoO3 has proven to be a more efficient cathode material than LaMnO3 at lower temperatures. In order to explain the difference in efficiency, we need to gain insight into the materials' properties at the atomic level. However, while LaMnO3 has been widely studied, ab initio studies on SmCoO3 are rare. Hence, in this paper, we perform a comparative DFT + U study of the structural, electronic, and magnetic properties of these two perovskites. To that end, we first determined a suitable Hubbard parameter for the Co d-electrons to obtain a proper description of SmCoO3 that fully agrees with the available experimental data. We next evaluated the impact of oxygen and cation vacancies on the geometry, electronic, and magnetic properties. Oxygen vacancies strongly alter the electronic and magnetic structures of SmCoO3, but barely affect LaMnO3. However, due to their high formation energy, their concentrations in the material are very low and need to be induced by doping. Studying the cation vacancy concentration showed that the formation of cation vacancies is less energetically favorable than oxygen vacancies and would thus not markedly influence the performance of the cathode.

  10. Micronucleus formation, DNA damage and repair in premenopausal women chronically exposed to high level of indoor air pollution from biomass fuel use in rural India.

    PubMed

    Mondal, Nandan Kumar; Mukherjee, Bidisha; Das, Debangshu; Ray, Manas Ranjan

    2010-03-29

    Genotoxicity of indoor air pollution from biomass fuel use has been examined in 132 biomass users (median age 34 years) and 85 age-matched control women from eastern India who used the cleaner fuel liquefied petroleum gas (LPG) to cook. Micronucleus (MN) frequency was evaluated in buccal (BEC) and airway epithelial cells (AEC); DNA damage was examined by comet assay in peripheral blood lymphocytes (PBL); and expressions of gamma-H2AX, Mre11 and Ku70 proteins were localized in AEC and PBL by immunocytochemistry. Reactive oxygen species (ROS) generation in leukocytes was measured by flow cytometry, and the levels of superoxide dismutase (SOD) and total antioxidant status (TAS) in blood were measured by spectrophotometry. Real-time aerosol monitor was used to measure particulate pollutants in indoor air. Compared with controls, biomass users had increased frequencies of micronucleated cells in BEC (3.5 vs. 1.7, p<0.001) and AEC (4.54 vs. 1.86, p<0.001), and greater comet tail % DNA (18.6 vs. 11.7%, p<0.01), tail length (45.5 vs. 31.4mum, p<0.01) and olive tail moment (4.0 vs. 1.4, p<0.01) in PBL. Moreover, biomass users had more gamma-H2AX-positive nuclei in PBL (49.5 vs. 8.5%, p<0.01) and AEC (11.3 vs. 2.9%, p<0.01) along with higher expression of DNA repair proteins Mre11 and Ku70 in these cells, suggesting stimulation of DNA repair mechanism. Biomass users showed rise in ROS generation and depletion of SOD and TAS. Biomass-using households had 2-4 times more particulate matter with diameter less than 10 and 2.5mum in indoor air, and MN frequency and comet tail % DNA were positively associated with these pollutants after controlling potential confounders. Thus, chronic exposure to biomass smoke causes chromosomal and DNA damage and upregulation of DNA repair mechanism.

  11. Fueling the central engine of radio galaxies. III. Molecular gas and star formation efficiency of 3C 293

    NASA Astrophysics Data System (ADS)

    Labiano, A.; García-Burillo, S.; Combes, F.; Usero, A.; Soria-Ruiz, R.; Piqueras López, J.; Fuente, A.; Hunt, L.; Neri, R.

    2014-04-01

    Context. Powerful radio galaxies show evidence of ongoing active galactic nuclei (AGN) feedback, mainly in the form of fast, massive outflows. But it is not clear how these outflows affect the star formation of their hosts. Aims: We investigate the different manifestations of AGN feedback in the evolved, powerful radio source 3C 293 and their impact on the molecular gas of its host galaxy, which harbors young star-forming regions and fast outflows of H i and ionized gas. Methods: We study the distribution and kinematics of the molecular gas of 3C 293 using high spatial resolution observations of the 12CO(1-0) and 12CO(2-1) lines, and the 3 mm and 1 continuum taken with the IRAM Plateau de Bure interferometer. We mapped the molecular gas of 3C 293 and compared it with the dust and star-formation images of the host. We searched for signatures of outflow motions in the CO kinematics, and re-examined the evidence of outflowing gas in the H i spectra. We also derived the star formation rate (SFR) and star formation efficiency (SFE) of the host with all available SFR tracers from the literature, and compared them with the SFE of young and evolved radio galaxies and normal star-forming galaxies. Results: The 12CO(1-0) emission line shows that the molecular gas in 3C 293 is distributed along a massive (M(H2) ~ 2.2 × 1010M⊙) ~24″(21 kpc-) diameter warped disk, that rotates around the AGN. Our data show that the dust and the star formation are clearly associated with the CO disk. The 12CO(2-1) emission is located in the inner 7 kpc (diameter) region around the AGN, coincident with the inner part of the 12CO(1-0) disk. Both the 12CO(1-0) and 12CO(2-1) spectra reveal the presence of an absorber against the central regions of 3C 293 that is associated with the disk. We do not detect any fast (≳500 km s-1) outflow motions in the cold molecular gas. The host of 3C 293 shows an SFE consistent with the Kennicutt-Schmidt law of normal galaxies and young radio galaxies, and it

  12. Hot-gas cleanup for molten carbonate fuel cells-dechlorination and soot formation. Final report, May 19, 1981-July 19, 1983

    SciTech Connect

    Ham, D.; Gelb, A.; Lord, G.; Simons, G.

    1984-01-01

    Two separate aspects of hot-gas conditioning for molten carbonate fuel cells (MCFC) were investigated under this contract: potential high temperature chloride sorbent materials were sreened and tested and carbon deposition on MCFC components was studied experimentally to determine guidelines for maximizing MCFC efficiency while avoiding carbon fouling. Natural minerals containing sodium carbonate were identified as the most promising candidates for economical removal of chlorides from coal gasifier effluents at temperatures of about 800 K (980/sup 0/F). The mineral Shortite was tested in a fixed bed and found to perform remarkably well with no calcination. Using Shortite we were able to achieve the program goal of less than 1 ppmV chlorides at 800 K. Shortite is an abundant mineral with no competing commercial demand, so it should provide an economical chloride cleanup sorbent. Measurements showed that carbon deposition can occur in the equilibrium carbon freee region because of the relative rates of the relevant reactions. On all surfaces tested, the Boudouard carbon formation reaction is much faster than the water-gas shift reaction which is much faster than the methanation reaction. This means that the normal practice of adding steam to prevent carbon formation will only succeed if flows are slow enough for the water shift reaction to go substantially to completion. More direct suppression of carbon formation can be achieved by CO/sub 2/ addition through anode recycle to force the Boudouard reaction backward. Addition of steam or CO/sub 2/ must be minimized to attain the highest possible MCFC efficiency. 28 references, 31 figures, 22 tables.

  13. Role of activation of protein kinase C in the stimulation of colonic epithelial proliferation and reactive oxygen formation by bile acids.

    PubMed Central

    Craven, P A; Pfanstiel, J; DeRubertis, F R

    1987-01-01

    Deoxycholate (DOC), chenodeoxycholate, 12-O-tetradecanoyl phorbol-13-acetate (TPA), or 1-oleoyl-2-acetyl-glycerol (OAG) activated colonic epithelial protein kinase C as reflected by translocation from the soluble to the particulate cell fraction. Activation of protein kinase C was correlated with stimulation of enhanced proliferative activity of colonic mucosa and reactive oxygen production. TPA and OAG, but not DOC, directly activated soluble protein kinase C in vitro. However, DOC rapidly increased labeled inositol phosphate and diacylglycerol accumulation in colonic epithelial cells. Retinoic acid inhibited protein kinase C activity and suppressed DOC-, TPA-, and OAG-induced increases in reactive oxygen production. The results support a role for protein kinase C in the stimulation of colonic epithelial proliferative activity and reactive oxygen production induced by bile acids, TPA and OAG. In contrast to TPA and OAG, which activate protein kinase C directly, bile acids appear to activate protein kinase C indirectly by increasing the diacylglycerol content of colonic epithelium. PMID:3027128

  14. FUEL ELEMENT FOR NUCLEAR REACTORS

    DOEpatents

    Bassett, C.H.

    1961-05-16

    A fuel element particularly adapted for use in nuclear reactors of high power density is offered. It has fissionable fuel pellet segments mounted in a tubular housing and defining a central passage in the fuel element. A burnable poison element extends through the central passage, which is designed to contain more poison material at the median portion than at the end portions thereby providing a more uniform hurnup and longer reactivity life.

  15. NUCLEAR FUEL MATERIAL

    DOEpatents

    Goeddel, W.V.

    1962-06-26

    An improved method is given for making the carbides of nuclear fuel material. The metal of the fuel material, which may be a fissile and/or fertile material, is transformed into a silicide, after which the silicide is comminuted to the desired particle size. This silicide is then carburized at an elevated temperature, either above or below the melting point of the silicide, to produce an intimate mixture of the carbide of the fuel material and the carbide of silicon. This mixture of the fuel material carbide and