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Sample records for reaction zone formations

  1. Fluid pressure and reaction zone formation at a lithological interface

    NASA Astrophysics Data System (ADS)

    Malvoisin, Benjamin; Podladchikov, Yuri

    2014-05-01

    Chemical composition variations in reaction zones between two distinct lithologies are generally interpreted in terms of chemical potential gradients and diffusion process. Concentration profiles can then be used to quantify the species diffusion coefficients or the time scale of geological events. However, chemical potential gradients are also functions of temperature and pressure and local variations of these parameters can thus potentially modify the diffusion process. In northern Corsica, a centimeter scale reaction zone formed under blueschist conditions at a serpentinite - marble contact of sedimentary origin. Three sub-zones having chemical compositions evolving from one rock end-member to another divide the reaction zone along sharp interfaces. At the reaction zone - marble interface, marble decarbonation occurs to form wollastonite and carbonaceous matter. Thermodynamic calculations for this reaction and the respective increase in density of 25 % and 7 % in the bulk rock and in the garnet minerals are interpreted as records of a pressure gradient during reaction zone formation. Moreover, the formation of a volatile-free sub-zone in the reaction zone from reaction between the H2O-bearing serpentinite and the CO2-bearing marble released fluids at the contact. The impact of such a release on the fluid pressure was modelled by considering the effects of both the rock compaction and the transport of fluid by hydraulic diffusion. Modelling results indicates that > 0.5 GPa fluid overpressure can be generated at the contact if devolatilization rates are of the order of the one experimentally measured (> 10-5 kg of fluid/m3 of rock/s). The resulting pressure gradient is of the order of magnitude of the one necessary to counter-balance the effect on chemical potential of the chemical composition variations across the contact. Finally, after the reaction has run to completion, the model predicts that fluid rapidly diffuses away from the interface which thus stops

  2. Prediction and characterization of heat-affected zone formation due to neighboring nickel-aluminum multilayer foil reaction

    SciTech Connect

    Adams, David P.; Hirschfeld, Deidre A.; Hooper, Ryan J.; Manuel, Michelle V.

    2015-09-01

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. Much of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To enhance the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical model for the purpose of evaluating new foil-substrate combinations for screening and optimization. The model is experimentally validated using a commercially available Ni-Al multilayer foils and different alloys.

  3. Treating tar sands formations with karsted zones

    SciTech Connect

    Vinegar, Harold J.; Karanikas, John Michael

    2010-03-09

    Methods for treating a tar sands formation are described herein. The tar sands formation may have one or more karsted zones. Methods may include providing heat from one or more heaters to one or more karsted zones of the tar sands formation to mobilize fluids in the formation. At least some of the mobilized fluids may be produced from the formation.

  4. Detonation Reaction Zones in Condensed Explosives

    SciTech Connect

    Tarver, C M

    2005-07-14

    Experimental measurements using nanosecond time resolved embedded gauges and laser interferometric techniques, combined with Non-Equilibrium Zeldovich--von Neumann--Doring (NEZND) theory and Ignition and Growth reactive flow hydrodynamic modeling, have revealed the average pressure/particle velocity states attained in reaction zones of self-sustaining detonation waves in several solid and liquid explosives. The time durations of these reaction zone processes is discussed for explosives based on pentaerythritol tetranitrate (PETN), nitromethane, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), triaminitrinitrobenzene(TATB) and trinitrotoluene (TNT).

  5. Treating nahcolite containing formations and saline zones

    DOEpatents

    Vinegar, Harold J

    2013-06-11

    A method for treating a nahcolite containing subsurface formation includes removing water from a saline zone in or near the formation. The removed water is heated using a steam and electricity cogeneration facility. The heated water is provided to the nahcolite containing formation. A fluid is produced from the nahcolite containing formation. The fluid includes at least some dissolved nahcolite. At least some of the fluid is provided to the saline zone.

  6. Three zones for illite formation during burial diagenesis and metamorphism

    USGS Publications Warehouse

    Eberl, D.D.

    1993-01-01

    Reinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K+. In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. -from Author

  7. Predicting km-scale shear zone formation

    NASA Astrophysics Data System (ADS)

    Gerbi, Christopher; Culshaw, Nicholas; Shulman, Deborah; Foley, Maura; Marsh, Jeffrey

    2015-04-01

    Because km-scale shear zones play a first-order role in lithospheric kinematics, accurate conceptual and numerical models of orogenic development require predicting when and where they form. Although a strain-based algorithm in the upper crust for weakening due to faulting appears to succeed (e.g., Koons et al., 2010, doi:10.1029/2009TC002463), a comparable general rule for the viscous crust remains unestablished. Here we consider two aspects of the geological argument for a similar algorithm in the viscous regime, namely (1) whether predicting km-scale shear zone development based on a single parameter (such as strain or shear heating) is reasonable; and (2) whether lithologic variability inherent in most orogenic systems precludes a simple predictive rule. A review of tectonically significant shear zones worldwide and more detailed investigations in the Central Gneiss belt of the Ontario segment of the Grenville Province reveals that most km-scale shear zones occur at lithological boundaries and involve mass transfer, but have fairly little else in common. As examples, the relatively flat-lying Twelve Mile Bay shear zone in the western Central Gneiss belt bounds the Parry Sound domain and is likely the product of both localized anatexis and later retrograde hydration with attendant metamorphism. Moderately dipping shear zones in granitoids of the Grenville Front Tectonic Zone apparently resulted from cooperation among several complementary microstructural processes, such as grain size reduction, enhanced diffusion, and a small degree of metamorphic reaction. Localization into shear zones requires the operation of some spatially restricted processes such as stress concentration, metamorphism/fluid access, textural evolution, and thermal perturbation. All of these could be due in part to strain, but not necessarily linearly related to strain. Stress concentrations, such as those that form at rheological boundaries, may be sufficient to nucleate high strain

  8. Prediction and characterization of heat-affected zone formation in tin-bismuth alloys due to nickel-aluminum multilayer foil reaction

    NASA Astrophysics Data System (ADS)

    Hooper, R. J.; Davis, C. G.; Johns, P. M.; Adams, D. P.; Hirschfeld, D.; Nino, J. C.; Manuel, M. V.

    2015-06-01

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. Most of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To improve the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical model for the purpose of predicting heat affected zone size in substrate materials. The model is experimentally validated using a commercially available Ni-Al multilayer foils and alloys from the Sn-Bi binary system. To accomplish this, phenomenological models for predicting the variation of physical properties (i.e., thermal conductivity, density, and heat capacity) with temperature and composition in the Sn-Bi system were utilized using literature data.

  9. Prediction and characterization of heat-affected zone formation in tin-bismuth alloys due to nickel-aluminum multilayer foil reaction

    DOE PAGESBeta

    Hooper, R. J.; Davis, C. G.; Johns, P. M.; Adams, D. P.; Hirschfeld, D.; Nino, J. C.; Manuel, M. V.

    2015-06-26

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. In this study, most of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To improve the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical modelmore » for the purpose of predicting heat affected zone size in substrate materials. The model is experimentally validated using a commercially available Ni-Al multilayer foils and alloys from the Sn-Bi binary system. To accomplish this, phenomenological models for predicting the variation of physical properties (i.e., thermal conductivity, density, and heat capacity) with temperature and composition in the Sn-Bi system were utilized using literature data.« less

  10. Prediction and characterization of heat-affected zone formation in tin-bismuth alloys due to nickel-aluminum multilayer foil reaction

    SciTech Connect

    Hooper, R. J.; Davis, C. G.; Johns, P. M.; Adams, D. P.; Hirschfeld, D.; Nino, J. C.; Manuel, M. V.

    2015-06-26

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. In this study, most of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To improve the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical model for the purpose of predicting heat affected zone size in substrate materials. The model is experimentally validated using a commercially available Ni-Al multilayer foils and alloys from the Sn-Bi binary system. To accomplish this, phenomenological models for predicting the variation of physical properties (i.e., thermal conductivity, density, and heat capacity) with temperature and composition in the Sn-Bi system were utilized using literature data.

  11. Diamond Formation in association with Deep Mantle Dehydration Zones

    NASA Astrophysics Data System (ADS)

    Harte, B.

    2009-12-01

    2SiO4 with and fPer + mpv indicate the preservation of UM/LM boundary reaction, which from experimental data is expected to be sharply constrained in depth, though the presence of H2O will broaden the reaction zone due to the potential stability of hydrous ringwoodite. Considerations of the preservation of hydrous peridotitic assemblages in subduction zones (Komabayashi, 2006, AGU monograph), show that an initially cool subducted slab may preserve hydrous assemblages to the lower part of the upper mantle and into the lower mantle. Here stagnation and warming of the slab may cause dehydration with the formation of fluids/melts which provide the potential location for diamond formation. At the top of the Transition Zone, Bercovici and Karato (2003, Nature 245) have suggested the existence of a melt zone. The location of this melt zone at its intersection with the upper surface of a subducting slab, provides an ideal location for the crystallisation of the majorite assemblages from around the top of the Transition Zone. This also accords with the crustal carbon isotope signatures in the host diamonds and the wide variations in REE abundances in the majorites. Deep diamond inclusions provide strong evidence for dehydration zones near the top and bottom of the Transition Zone.

  12. Production from multiple zones of a tar sands formation

    DOEpatents

    Karanikas, John Michael; Vinegar, Harold J

    2013-02-26

    A method for treating a tar sands formation includes providing heat to at least part of a hydrocarbon layer in the formation from a plurality of heaters located in the formation. The heat is allowed to transfer from the heaters to at least a portion of the formation. Fluids are produced from the formation through at least one production well that is located in at least two zones in the formation. The first zone has an initial permeability of at least 1 darcy. The second zone has an initial of at most 0.1 darcy. The two zones are separated by a substantially impermeable barrier.

  13. Detonation Reaction Zone Measurements of PBX 9501 and PBX 9502

    NASA Astrophysics Data System (ADS)

    Vincent, Samuel; Short, Mark; Jackson, Scott

    2013-06-01

    Explosives are often confined by inert materials. During detonation, the high pressures associated with the detonation reaction zone and expansion of products induce motion in the confiner. Classical programmed burn models for conventional high explosives (CHEs) performance do not aim to accurately capture the contribution to CHE drive from the short (100-200 micron) detonation reaction zone, as the drive is dominated by expansion of detonation products. However, the reaction zone lengths of insensitive (millimeter-scale) and non-ideal explosives (millimeter-to-centimeter-scale) are long enough that a significant contribution to the HE work on the confiner occurs within the reaction zone. Thus accurate prediction of the reaction zone flow structure and mechanical state is crucial to accurately model the motion of confiners driven by insensitive and non-ideal explosives. In this work, we have measured particle velocity profiles of detonation reaction zones in PBX 9501 and PBX 9502 slab geometries at the breakout surface using PDV imaging through LiF windows. We compare this data to model predictions in the slab geometry using the Wescott-Stewart-Davis reactive burn model and comment on the model performance.

  14. Varying heating in dawsonite zones in hydrocarbon containing formations

    DOEpatents

    Vinegar, Harold J.; Xie, Xueying; Miller, David Scott

    2009-07-07

    A method for treating an oil shale formation comprising dawsonite includes assessing a dawsonite composition of one or more zones in the formation. Heat from one or more heaters is provided to the formation such that different amounts of heat are provided to zones with different dawsonite compositions. The provided heat is allowed to transfer from the heaters to the formation. Fluids are produced from the formation.

  15. Excavation Damaged Zones In Rock Salt Formations

    SciTech Connect

    Jockwer, N.; Wieczorek, K.

    2008-07-01

    Salt formations have long been proposed as potential host rocks for nuclear waste disposal. After the operational phase of a repository the openings, e.g., boreholes, galleries, and chambers, have to be sealed in order to avoid the release of radionuclides into the biosphere. For optimising the sealing techniques knowledge about the excavation damaged zones (EDZ) around these openings is essential. In the frame of a project performed between 2004 and 2007, investigations of the EDZ evolution were performed in the Stassfurt halite of the Asse salt mine in northern Germany. Three test locations were prepared in the floor of an almost 20 year old gallery on the 800-m level of the Asse mine: (1) the drift floor as existing, (2) the new drift floor shortly after removing of a layer of about 1 m thickness of the floor with a continuous miner, (3) the new drift floor 2 years after cutting off the 1-m layer. Subject of investigation were the diffusive and advective gas transport and the advective brine transport very close to the opening. Spreading of the brine was tracked by geo-electric monitoring in order to gain information about permeability anisotropy. Results obtained showed that EDZ cut-off is a useful method to improve sealing effectiveness when constructing technical barriers. (authors)

  16. Stability of sharp reaction fronts in porous rocks and implications for non-sharp reaction zones

    NASA Astrophysics Data System (ADS)

    Wangen, Magnus

    2014-05-01

    The flow of reactive fluids in the subsurface, like for instance acids, may create reaction fronts. A sharp reaction front is an idealization of the narrow zone where the reaction takes place. Narrow reaction zones are studied with a one-component reaction transport model, where a first order reaction changes the porosity. The porosity field is coupled to the permeability field, where an increasing porosity leads to an increasing permeability. Therefore, the reaction has a feed-back on the flow field. We have derived 1D approximate solutions for the change in concentration and porosity across the reaction zone. These solutions are used to derive a condition for reaction fronts to be narrow. The condition gives a minimum reaction rate necessary for 90% of the reaction to be restricted to the given area. Sharp fronts are idealizations of narrow fronts that are more amendable for analytical treatment. A condition has recently been derived for the stability of sharp reaction fronts in homogeneous porous medium using linear stability analysis. The condition gives that a perturbation of a flat reaction front of any wave-length becomes unstable if the permeability behind the front increases. The front instability grows faster for short wave lengths than for long wave lengths. Similarly, the perturbations of the front will die out if the permeability behind the front decreases, and short wave length perturbations will die out faster than long wave length perturbations. It is a condition that applies for both 2D and 3D porous media. Numerical experiments are shown that demonstrate the front stability criterion, when the fronts are narrow, but not sharp. The sharp front approximation turns out to be useful for the interpretation of reactions that are not sufficiently fast to give narrow reaction zones, when the reaction alters the porosity- and the permeability fields. Dissolution is an important example of reactions that increase the porosity and therefore the permeability

  17. A library of prompt detonation reaction zone data

    SciTech Connect

    Souers, P. C., LLNL

    1998-06-01

    Tables are given listing literature data that allows calculation of sonic reaction zones at or near steady-state for promptly detonating explosive cylinders. The data covers homogeneous, heterogeneous, composite, inorganic and binary explosives and allows comparison across the entire explosive field. Table 1 lists detonation front curvatures. Table 2 lists Size Effect data, i.e. the change of detonation velocity with cylinder radius. Table 3 lists failure radii and detonation velocities. Table 4 lists explosive compositions. A total of 51 references dating back into the 1950`s are given. Calculated reaction zones, radii of curvature and growth rate coefficients are listed.

  18. Aquifer/aquitard interfaces: Mixing zones that enhance biogeochemical reactions

    USGS Publications Warehouse

    McMahon, P.B.

    2001-01-01

    Several important biogeochemical reactions are known to occur near the interface between aquifer and aquitard sediments. These reactions include O2 reduction; denitrification; and Fe3+, SO42-, and CO2 (methanogenesis) reduction. In some settings, these reactions occur on the aquitard side of the interface as electron acceptors move from the aquifer into the electron-donor-enriched aquitard. In other settings, these reactions occur on the aquifer side of the interface as electron donors move from the aquitard into the electron-acceptor-enriched, or microorganism-enriched, aquifer. Thus, the aquifer/aquitard interface represents a mixing zone capable of supporting greater microbial activity than either hydrogeologic unit alone. The extent to which biogeochemical reactions proceed in the mixing zone and the width of the mixing zone depend on several factors, including the abundance and solubility of electron acceptors and donors on either side of the interface and the rate at which electron acceptors and donors react and move across the interface. Biogeochemical reactions near the aquifer/aquitard interface can have a substantial influence on the chemistry of water in aquifers and on the chemistry of sediments near the interface.

  19. Audience Reactions to Two Visual Formats.

    ERIC Educational Resources Information Center

    Ramsey, Richard David

    One hundred undergraduate business students completed a questionnaire designed to determine their reactions to a traditional and a "flashier" textbook format. Before completing the questionnaire, subjects spent several minutes examining two business textbooks--one an older textbook with black ink on white paper, narrow margins, and few…

  20. Reaction front formation in contaminant plumes

    NASA Astrophysics Data System (ADS)

    Cribbin, Laura B.; Winstanley, Henry F.; Mitchell, Sarah L.; Fowler, Andrew C.; Sander, Graham C.

    2014-12-01

    The formation of successive fronts in contaminated groundwater plumes by subsoil bacterial action is a commonly accepted feature of their propagation, but it is not obviously clear from a mathematical standpoint quite how such fronts are formed or propagate. In this paper we show that these can be explained by combining classical reaction-diffusion theory involving just two reactants (oxidant and reductant), and a secondary reaction in which a reactant on one side of such a front is (re-)formed on the other side of the front via diffusion of its product across the front. We give approximate asymptotic solutions for the reactant profiles, and the propagation rate of the front.

  1. Fluid-rock reaction weakening of fault zones

    SciTech Connect

    Wintsch, R.P.; Christoffersen, R.; Kronenberg, A.K.

    1995-07-10

    The presence of weak phyllosilicates may explain the low shear strengths of fault zones if they define well-developed fabrics. The growth of phyllosilicates is favored in meteoric water-dominated granitic fault systems, where mineral-aqueous fluid equilibria predict that modal phyllosilicate will increase via feldspar replacement reactions. In deeper, more alkaline, rock-dominated regimes, the reactions reverse, and feldspars tend to replace phyllosilicates. In Mg-rich mafic rocks, however, phyllosilicates (chlorite, biotite) can replace stronger framework and chain silicates in both shallower (<{approximately}10 km) meteoric H{sub 2}O-dominated and in deeper, alkaline, rock-dominated regimes. Where these phyllosilicates precipitate in active fault zones, they contribute directly to reaction softening. Because low-temperature deformation of phyllosilicates is not governed by frictional processes alone but can occur by pressure-independent dislocation glide, the strength of phyllosilicate-rich fault rocks can be low at all depths. Low strain rate creep during interseismic periods can align phyllosilicate grains in foliated gouge and phyllonites. Where preferred orientations are strong and contiguity of phyllosilicates is large, strengths of rocks within fault zones may approach minimum strengths defined by single phyllosilicate crystals. Fault zones containing localized high concentrations of phyllosilicates with strong preferred orientations in well-defined folia can exhibit aseismic slip, especially where mafic Mg-rich rocks occur along the fault (like parts of the San Andreas Fault). 104 refs., 6 figs., 1 tab.

  2. Metasomatic reaction bands at the Mt. Hochwart gneiss-peridotite contact (Ulten Zone, Italy): insights into fluid-rock interaction in subduction zones

    NASA Astrophysics Data System (ADS)

    Marocchi, M.; Mair, V.; Tropper, P.; Bargossi, G. M.

    2009-03-01

    We investigated the contact zone between peridotite lenses and host gneisses located on the northern side of the Hochwart peak, also known as Vedetta Alta (Ulten Zone, Alto Adige -Südtirol) where metasomatic contact bands occur. The country rocks are gneisses consisting mainly of quartz, K-feldspar, garnet, kyanite, biotite and muscovite. The ultramafic body consists of a hectometre-sized garnet peridotite and harzburgite lens. The reaction zone shows mineralogic zoning from phlogopite-rich to tremolite-anthophyllite-talc-rich rocks from the host gneiss towards the peridotite. In some cases, lenses of serpentine and talc in association with chlorite, and trondhjemitic pods develop at the ultramafic rocks border to the gneisses. Trondhjemite dikes with pegmatoid texture also crosscut the peridotite body. Phlogopite aggregates with accessory zircon, Cl-apatite and tourmaline and phlogopite-hornblende aggregates also occur. The combination of petrography, mineral chemistry and mass balance calculations constrains the gains and losses of elements during metasomatism. Reaction zone formation involved extensive addition of H2O, K2O and LILE from the fluid, whereas MgO, CaO and Al2O3 were removed from the peridotite. Thus, the formation of the reaction zones between the mantle rocks and the gneisses was triggered by considerable fluid/melt circulation, causing crystallisation of mainly phlogopite, anthophyllite and talc, and the release of a trondhjemitic residual melt. Field mapping provides evidence that the internal structures of the host migmatites (folds) and those of the peridotites (foliation, fluid texture) are discordant. Pseudosection calculations give insights into the P-T conditions (T 660-700°C; P 0.5-0.7 GPa) of metasomatism responsible for the formation of reaction zones, which is related to the retrograde path of the Ulten Zone peridotites. Our results suggest that the redistribution of major and trace elements in subduction zones is strongly influenced

  3. Reaction front formation in contaminant plumes.

    PubMed

    Cribbin, Laura B; Winstanley, Henry F; Mitchell, Sarah L; Fowler, Andrew C; Sander, Graham C

    2014-12-15

    The formation of successive fronts in contaminated groundwater plumes by subsoil bacterial action is a commonly accepted feature of their propagation, but it is not obviously clear from a mathematical standpoint quite how such fronts are formed or propagate. In this paper we show that these can be explained by combining classical reaction-diffusion theory involving just two reactants (oxidant and reductant), and a secondary reaction in which a reactant on one side of such a front is (re-)formed on the other side of the front via diffusion of its product across the front. We give approximate asymptotic solutions for the reactant profiles, and the propagation rate of the front. PMID:25461883

  4. Density Effect on Detonation Reaction Zone Length in Solid Explosives

    NASA Astrophysics Data System (ADS)

    Lubyatinsky, S. N.; Loboiko, B. G.

    1997-07-01

    Density effect on detonation reaction zone length have been studied on RDX and PETN using a photoelectric technique to record the radiation intensity history of the shock front in chloroform placed on the charge face. Charge density was found to drastically affect the reaction zone length as well as the charge appearance. The charges pressed to 0.92 of crystal density were completely opaque and exhibited the von Neumann spike of 0.3 mm in length, typical for high explosives. The charges solvent-pressed to 0.99 of crystal density were agated (semi-transparent, resembling agates) and did not exhibited the von Neumann spike, which implies that its length did not exceed 0.03 mm. The following explanation was offered. In agated, practically non-porous, charges the detonation front is a strong plane shock inducing almost instant reaction. In charges consisting of separate crystals the detonation front becomes three-dimensional. As a result some fraction of explosive is compressed by a sequence of shocks almost isentropically and reacts relatively slowly, so that it can be measured.

  5. Effect of primary-zone equivalence ratio on pollutant formation

    NASA Technical Reports Server (NTRS)

    Claus, R. W.

    1979-01-01

    Test were conducted to determine the effect of primary-zone equivalence ratio on the formation of smoke and other gaseous pollutants in an experimental can combustor. Several fuel injection techniques were examined at primary-zone equivalence ratios from 0.8 to 2.0. The main emphasis was on reducing fuel-rich-combustion smoke levels. Two of the four fuel injection configurations studied produced smoke levels below a smoke number of 20 at a primary-zone equivalence ratio of about 1.7. As the fuel mixing and atomization were recorded at primary-zone equivalence ratios as high as 2.0. The gaseous emissions of unburned hydrocarbons, carbon monoxide, and oxides of nitrogen were quite sensitive to the fuel injection configuration as well as to the primary-zone equilvalence ratio.

  6. Convection associated with exclusion zone formation in colloidal suspensions.

    PubMed

    Musa, Sami; Florea, Daniel; Wyss, Hans M; Huyghe, Jacques M

    2016-01-28

    The long-range repulsion of colloids from various interfaces has been observed in a wide range of studies from different research disciplines. This so-called exclusion zone (EZ) formation occurs near surfaces such as hydrogels, polymers, or biological tissues. It was recently shown that the underlying physical mechanism leading to this long-range repulsion is a combination of ion-exchange at the interface, diffusion of ions, and diffusiophoresis of colloids in the resulting ion concentration gradients. In this paper, we show that the same ion concentration gradients that lead to exclusion zone formation also imply that diffusioosmosis near the walls of the sample cell must occur. This should lead to convective flow patterns that are directly associated with exclusion zone formation. We use multi-particle tracking to study the dynamics of particles during exclusion zone formation in detail, confirming that indeed two pronounced vortex-like convection rolls occur near the cell walls. These dramatic flow patterns persist for more than 4 hours, with the typical velocity decreasing as a function of time. We find that the flow velocity depends strongly on the surface properties of the sample cell walls, consistent with diffusioosmosis being the main physical mechanism that governs these convective flows. PMID:26616213

  7. FORMATION OF CIRCUMBINARY PLANETS IN A DEAD ZONE

    SciTech Connect

    Martin, Rebecca G.; Armitage, Philip J.; Alexander, Richard D.

    2013-08-10

    Circumbinary planets have been observed at orbital radii where binary perturbations may have significant effects on the gas disk structure, on planetesimal velocity dispersion, and on the coupling between turbulence and planetesimals. Here, we note that the impact of all of these effects on planet formation is qualitatively altered if the circumbinary disk structure is layered, with a non-turbulent midplane layer (dead zone) and strongly turbulent surface layers. For close binaries, we find that the dead zone typically extends from a radius close to the inner disk edge up to a radius of around 10-20 AU from the center of mass of the binary. The peak in the surface density occurs within the dead zone, far from the inner disk edge, close to the snow line, and may act as a trap for aerodynamically coupled solids. We suggest that circumbinary planet formation may be easier near this preferential location than for disks around single stars. However, dead zones around wide binaries are less likely, and hence planet formation may be more difficult there.

  8. Aquifer/aquitard interfaces: mixing zones that enhance biogeochemical reactions

    NASA Astrophysics Data System (ADS)

    McMahon, P. B.

    2001-01-01

    Several important biogeochemical reactions are known to occur near the interface between aquifer and aquitard sediments. These reactions include O2 reduction; denitrification; and Fe3+, SO42-, and CO2 (methanogenesis) reduction. In some settings, these reactions occur on the aquitard side of the interface as electron acceptors move from the aquifer into the electron-donor-enriched aquitard. In other settings, these reactions occur on the aquifer side of the interface as electron donors move from the aquitard into the electron-acceptor-enriched, or microorganism-enriched, aquifer. Thus, the aquifer/aquitard interface represents a mixing zone capable of supporting greater microbial activity than either hydrogeologic unit alone. The extent to which biogeochemical reactions proceed in the mixing zone and the width of the mixing zone depend on several factors, including the abundance and solubility of electron acceptors and donors on either side of the interface and the rate at which electron acceptors and donors react and move across the interface. Biogeochemical reactions near the aquifer/aquitard interface can have a substantial influence on the chemistry of water in aquifers and on the chemistry of sediments near the interface. Résumé. Il se produit au voisinage de l'interface entre les aquifères et les imperméables plusieurs réactions biogéochimiques importantes. Il s'agit des réactions de réduction de l'oxygène, de la dénitrification et de la réduction de Fe3+, SO42- et CO2 (méthanogenèse). Dans certaines situations, ces réactions se produisent du côté imperméable de l'interface, avec des accepteurs d'électrons qui vont de l'aquifère vers l'imperméable riche en donneurs d'électrons. Dans d'autres situations, ces réactions se produisent du côté aquifère de l'interface, avec des donneurs d'électrons qui se déplacent de l'imperméable vers l'aquifère riche en accepteurs d'électrons ou en microorganismes. Ainsi, l'interface aquif

  9. Pseudo-Reaction Zone model calibration for Programmed Burn calculations

    NASA Astrophysics Data System (ADS)

    Chiquete, Carlos; Meyer, Chad D.; Quirk, James J.; Short, Mark

    2015-06-01

    The Programmed Burn (PB) engineering methodology for efficiently calculating detonation timing and energy delivery within high explosive (HE) engineering geometries separates the calculation of these two core components. Modern PB approaches utilize Detonation Shock Dynamics (DSD) to provide accurate time-of-arrival information throughout a given geometry, via an experimentally calibrated propagation law relating the surface normal velocity to its local curvature. The Pseudo-Reaction Zone (PRZ) methodology is then used to release the explosive energy in a finite span following the prescribed arrival of the DSD propagated front through a reactive, hydrodynamic calculation. The PRZ energy release rate must be coupled to the local burn velocity set by the DSD surface evolution. In order to synchronize the energy release to the attendant timing calculation, detonation velocity and front shapes resulting from reactive burn simulations utilizing the PRZ rate law and parameters will be fitted to analogues generated via the applied DSD propagation law, thus yielding the PRZ model calibration for the HE.

  10. Horizontal shear zones: physical modeling of formation and structure

    NASA Astrophysics Data System (ADS)

    Bokun, A. N.

    2009-11-01

    On examples of ductile viscous materials (pastes), which demonstrated the deformational type of coagulation behavior and the reproduced zones of the horizontal shear of a brittle fracture, ductile flow, and intermediate types. The formation of coagulation agglomerates appeared well organized, both in terms of time and structurally. The found systems of fractures revealed a sequential course of the deformation process and the contribution of each system in the total structural transformation was established. By virtue of rheological analysis of coagulation structures, the basic parameters (yield strength, viscosity), and their input into the model of the deformational response (brittle, ductile), were determined. The substantial composition and its deformational properties of the material under question appeared to dictate the structure of shear zones and their general mutual organization. The rheological analysis of coagulation clusters of model materials allowed for the justified interpretation of experimental data to regulate deformation processes effectively and predict their results.

  11. Mechanism of décollement formation in subduction zones

    NASA Astrophysics Data System (ADS)

    Hori, Takane; Sakaguchi, Hide

    2011-12-01

    The mechanism of décollement formation was investigated through a particle-based simulation model assuming homogeneity (e.g. no weak layer or pore fluid). A décollement-like structure appeared as a spontaneously localized shear deformation near the bottom of the sediment when the thickness of the sediment was sufficient to balance the gravitational force and tectonic loading. In contrast, no such décollement-like structure was formed when the sediment was too thin; in this case, the entire prism was deformed because of plate motion. These results are consistent with various observations in real subduction zones. A precise analysis of the stress state evolution during accretion reveals that the formation of a décollement-like structure is controlled by the spatio-temporal distribution of isotropic compression states.

  12. Understanding Mechanisms of Rind Formation in Mélange Zones using Highly Siderophile Elements

    NASA Astrophysics Data System (ADS)

    Gorman, J. K.; Penniston-Dorland, S. C.; Walker, R. J.; Marschall, H. R.

    2012-12-01

    Two mechanisms have previously been proposed for the formation of reaction zones found between mafic and ultramafic rocks in mélange zones. These mechanisms are fluid-assisted metasomatism (transport by fluid flow or by diffusion through an intergranular fluid) and tectonic mixing. We are currently studying the highly siderophile element (HSE) compositions of mafic and ultramafic rocks and reaction zones from several different high P/T metamorphic complexes, including the Catalina Schist (Santa Catalina Island, CA), the Cycladic Complex (Syros, Greece), the Samana Metamorphic Complex (Dominican Republic), and the Franciscan Complex (CA). The mafic rocks in all localities have high 187Os/188Os and low Os, Ir and Ru concentrations, consistent with basaltic protoliths. The more mantle-like rocks (serpentinite, mélange matrix) and the reaction zones have lower 187Os/188Os, and higher Os, Ir and Ru concentrations. Here we report data from traverses across two reaction features: one from the Catalina Schist, the other from the Cycladic complex. The Catalina traverse consists of twelve samples along 30cm between an amphibolite-grade mafic block and its reaction rind (actinolite-chlorite schist) adjacent to ultramafic-rich matrix. The traverse from Syros consists of five samples along 165cm between blueschist-grade metamorphosed volcaniclastic (basaltic to intermediate) tuffs and a >50 m serpentinite lens between which there is a 1-2m thick reaction blackwall zone dominantly consisting of chlorite schist. Samples of the Catalina rind are enriched in whole-rock SiO2, K2O, Rb, Ba, MgO, Cr, Ni, Os, Ir, and Ru relative to samples of the block core, and are depleted in FeO, Al2O3, TiO2, CaO, and Zr. 187Os/188Os ratios are distinctly lower in the rind (0.13 to 0.18) compared to the block (0.43 to 2.23). The Syros blackwall has elevated MgO, CaO, Cr and Ni relative to the non-metasomatised assemblage, while there is depletion of Rb, Ba, and K2O. The HSE concentrations are

  13. [Formations and reactions of aromatic furazan compounds].

    PubMed

    Hasegawa, M; Takabatake, T; Miyazawa, T

    2001-06-01

    A reaction from various kinds of nitroquinoline with hydroxylamine in potassium hydroxide alkalinity produced a novel product, furazanoquinoline, besides the known amino derivatives. The products obtained were furazano [3,4-f] quinoline (5) from 5-nitroquinoline (1) and 6-nitroquinoline (6), and furazano [3,4-h] quinoline (10) from 7-nitroquinoline (8) and 8-nitroquinoline (11). The reaction mechanism was believed to be as shown in Figs. 2 and 3. The photoreaction of benzofuroxan (19) in acetonitrile containing a little water, under a high pressure mercury lamp, produced 1H-azepine-2,7-dione (20), while under irradiation using a low pressure lamp, 6H-furazano [4,5-c] carbazole-3-oxide (21) and compound 20 were obtained. Then the photoproduct 20 produced photodimer 22 by irradiation in acetonitrile: water (9:1, v/v) using a high or low pressure mercury lamp, while photolysis with alkali proceeded as in the photoreaction of N-alkylimide to give 7-hydroxy-1H-azepine-2-one (23). When pyrido [2,3-c] furoxan (24) was irradiated in acetonitrile containing a little water with a low pressure mercury lamp, 3-nitro-2-pyridone (25) was obtained. When compound 24 was irradiated in the presence of morpholine with a low pressure mercury lamp in an argon atmosphere, 6-morpholinopyridine 2,3-dioxime (26) was produced. Quinoxaline 1,4-dioxide derivatives (31, 33), phenazine 5,10-dioxide derivatives (36, 37) and pyrido [2,3-b] pyrazine derivatives (38, 39) were synthesized from the corresponding furoxan catalyzed by silica gel or molecular sieves, and their antibacterial properties were evaluated. The results of antibacterial screening tests in vitro, revealed strong activity against Bacteroides fragilis. PMID:11433773

  14. Reaction zone microstructure in a Ti3Al + Nb/SiC composite

    NASA Technical Reports Server (NTRS)

    Baumann, S. F.; Smith, S. D.; Brindley, P. K.

    1990-01-01

    A composite of Ti-25Al-13Nb (atomic percent) matrix with a continuous SiC fiber (SCS-6) reinforcement was fabricated by hot pressing powder cloths and mats of fiber. The fiber/matrix reaction zone was studied using scanning electron microscopy (SEM) and transmission electron microscopy/analytical electron microscopy (TEM/AEM) techniques. The extent of reaction was determined, phases were identified, and solute partitioning among the phases was determined. It was found that the matrix had reacted only with a portion of the carbon-rich outer layer of the SCS-6 fiber. The reaction zone contained two concentric zones which are distinguished by the presence of different carbide phases. Both zones contained a hexagonal Si-bearing phase, and one of the zones also contained some fine scattered porosity. The results are discussed with reference to available phase equilibria data.

  15. Formation of mesic nuclei by (γ,p) reactions

    NASA Astrophysics Data System (ADS)

    Nagahiro, H.; Jido, D.; Hirenzaki, S.

    2005-10-01

    We present a theoretical study on formation rates of η and ω meson-nucleus systems induced by (γ,p) reactions on nuclear targets at ideal recoilless condition. We find that the smaller distortion effect in the (γ,p) reaction enables us to investigate properties of the mesons created deeply inside nucleus more clearly. We also consider excitation of scalar-isoscalar (σ) mode in nucleus in order to investigate spectral enhancement around two-pion threshold caused by partial restoration of chiral symmetry. We conclude that valuable information of meson-nucleus interactions can be extracted from global structure of the missing mass spectra in the (γ,p) reaction.

  16. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  17. Periodic Vesicle Formation in Tectonic Fault Zones--an Ideal Scenario for Molecular Evolution.

    PubMed

    Mayer, Christian; Schreiber, Ulrich; Dávila, María J

    2015-06-01

    Tectonic fault systems in the continental crust offer huge networks of interconnected channels and cavities. Filled mainly with water and carbon dioxide (CO2), containing a wide variety of hydrothermal chemistry and numerous catalytic surfaces, they may offer ideal reaction conditions for prebiotic chemistry. In these systems, an accumulation zone for organic compounds will develop at a depth of approximately 1 km where CO2 turns sub-critical and dissolved components precipitate. At this point, periodic pressure changes caused for example by tidal influences or geyser activity may generate a cyclic process involving repeated phase transitions of carbon dioxide. In the presence of amphiphilic compounds, this will necessarily lead to the transient formation of coated water droplets in the gas phase and corresponding vesicular structures in the aqueous environment. During this process, the concentration of organic components inside the droplets and vesicles would be drastically increased, allowing for favorable reaction conditions and, in case of the vesicles generated, large trans-membrane concentration gradients. Altogether, the process of periodic formation and destruction of vesicles could offer a perfect environment for molecular evolution in small compartments and for the generation of protocells. The basic process of vesicle formation is reproduced experimentally with a lipid in a water/CO2 system. PMID:25716918

  18. Formation of superheavy nuclei in cold fusion reactions

    SciTech Connect

    Feng Zhaoqing; Jin Genming; Li Junqing; Scheid, Werner

    2007-10-15

    Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus, and the de-excitation process are calculated by using an empirical coupled channel model, solving a master equation numerically and applying statistical theory, respectively. Evaporation residue excitation functions in cold fusion reactions are investigated systematically and compared with available experimental data. Maximal production cross sections of superheavy nuclei in cold fusion reactions with stable neutron-rich projectiles are obtained. Isotopic trends in the production of the superheavy elements Z=110, 112, 114, 116, 118, and 120 are analyzed systematically. Optimal combinations and the corresponding excitation energies are proposed.

  19. Metasomatic Reaction Zones as Monitors of Trace Element Transfer at the Slab-Mantle Interface: the Case of the Hochwart Peridotite (Ulten Zone, Italy)

    NASA Astrophysics Data System (ADS)

    Marocchi, M.; Hermann, J.; Bargossi, G. M.; Mair, V.; Morten, L.

    2006-12-01

    Ultramafic blocks belonging to the Hochwart peridotite outcrop (Ulten Zone, Italian Alps) preserve a series of metasomatic mineral zones generated by infiltration of Si-rich hydrous fluids which occurred at the gneiss- peridotite interface. The age of the high pressure metamorphism for the Hochwart complex has been constrained at 330 Ma (Tumiati et al., 2003, EPSL, 210, 509-526). The country rocks are stromatic gneisses consisting mainly of quartz, K-feldspar, garnet, kyanite, biotite and muscovite. The ultramafic body consists of strongly serpentinized metaperidotites which are exposed as a hectometre-size lens along a steep gully, associated to monomineralic zones that developed at the contact between the peridotite body and the garnet gneiss country rocks. The composition of the metasomatic zones has been investigated in detail and records an order of metasomatic zoning formed by phlogopite-rich to tremolite-anthophyllite-rich rocks going from the host gneiss towards the peridotite. In some cases, the ultramafics fade into the gneisses developing serpentine and talc which has replaced, presumably at lower temperatures, the serpentine matrix and occurs in association with chlorite. Phlogopite aggregates (phlogopitite) with accessory minerals (quartz + zircon + apatite) and metabasic pods (phlogopite and hornblende) also occur. Black tourmaline (schorl-dravite solid solution) has been found for the first time in the contact near the phlogopite zone, suggesting an external addition of elements (boron and fluorine) to the system at high temperature. The formation of the metasomatic zones composed exclusively of hydrous phases must have involved extensive H2O-metasomatism as already documented for the Ulten peridotites. The source for these fluids can be a system of trondhjemitic-pegmatitic dikes cutting the peridotite that would have channelled aqueous fluids into the ultramafic rocks. Whole-rock geochemistry and trace element (LA ICP-MS) composition of hydrous

  20. Determining the mechanical strength of CO2-induced reaction zones in wellbore cement: is it worth it?

    NASA Astrophysics Data System (ADS)

    Hangx, Suzanne; Marcelis, Fons; van der Linden, Arjan; Liteanu, Emilia

    2015-04-01

    CO2 injection, either for long-term CO2 storage (CCS) or Enhanced Oil Recovery (EOR), strongly hinges on maintaining storage integrity. Injection and legacy wells penetrating the caprock pose one of the most likely points of leakage. In order to be able to predict the long-term integrity of such wellbores, it's important to understand their chemical, hydrological and mechanical behaviour, and how it may change due to CO2 exposure. Generally, in response to CO2/brine/cement interactions, a number of different reaction zones are observed, each with their own chemical, and hence mechanical, signature. To aid mechanical modelling efforts, assessing the risk of cement failure caused by stress and temperature changes, knowledge is required of the strength of each of these zones. We performed experiments on Class G Portland cement to investigate the chemical-mechanical coupling due to CO2-exposure. Batch reaction experiments, in the presence of CO2-rich brine, were performed under typical storage conditions (T = 65° C, PCO2 = 8 MPa) for various periods of time (1, 2, 3, 4, 5 and 6 months). After exposure, mechanical tests were performed on the observed reaction zones, using the so-called core scratching technique, to evaluate the unconfined compressive strength (UCS) as a function of exposure time. Chemical analyses (CT-imaging, SEM microscopy, EDX chemical analysis) showed the formation of three reaction zones, similarly to what has been observed in other studies. Measurements of the mechanical strength of these different zones showed highly variable results. Such variations have also been observed in other studies, using different measurement techniques. The large variability in strength measurements is most likely an inherent result of the heterogenic nature of cement, which affects the extent and location of reaction throughout the sample. This begs the question: is it worth studying the mechanical strength of reaction-induced zones in cement? Or will it suffice to

  1. Ignition and Growth Modeling of Detonation Reaction Zone Experiments on Single Crystals of PETN and HMX

    NASA Astrophysics Data System (ADS)

    White, Bradley; Tarver, Craig

    2015-06-01

    Fedorov et al. reported nanosecond time resolved interface particle velocity records for detonation reaction zone profiles of single crystals of PETN and HMX with adjoining LiF windows. Von Neumann spike and Chapman-Jouguet pressures were measured, and reaction zone lengths and times wereinferred. The single crystal detonation velocities and von Neumann spike pressures are higher than those measured for heterogeneous PETN and HMX-based explosives pressed to 98-99% theoretical maximum density. Due to the absence of voids, the single crystal detonation reaction zone lengths and times for both PETN and HMX were longer than those for their heterogeneous explosives. Ignition and Growth modeling results are compared to the single crystal PETN and HMX measurements and to previous experimental results for pressed PETN and HMX charges. This work was performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344.

  2. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation.

    PubMed

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T; Crowley, Michael F

    2016-06-15

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the α-O cleavage reaction is lower than that of the β-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets. PMID:27236926

  3. Groundwater compatibility with formation water and pay zone rocks in Pervomaysk oil-gas-condensate field to maintain formation pressure

    NASA Astrophysics Data System (ADS)

    Trifonov, N.; Nazarov, A.; Alekseev, S.

    2016-03-01

    The paper describes the research results in determining the compatibility of groundwater from Aptain-Albian-Cenomanian aquifer with formation water and pay zone rocks in U1 layer sediments, Pervomaysk oil field.

  4. f 1 (1285) formation in photon-photon fusion reactions

    NASA Astrophysics Data System (ADS)

    Aihara, H.; Alston-Garnjost, M.; Avery, R. E.; Barbaro-Galtieri, A.; Barker, A. R.; Barnett, B. A.; Bauer, D. A.; Bay, A.; Bengtsson, H.-U.; Bobbink, G. J.; Buchanan, C. D.; Buijs, A.; Caldwell, D. O.; Chao, H.-Y.; Chun, S.-B.; Clark, A. R.; Cowan, G. D.; Crane, D. A.; Dahl, O. I.; Daoudi, M.; Derby, K. A.; Eastman, J. J.; Eberhard, P. H.; Edberg, T. K.; Eisner, A. M.; Enomoto, R.; Erné, F. C.; Fairfield, K. H.; Hauptman, J. M.; Hofmann, W.; Hylen, J.; Kamae, T.; Kaye, H. S.; Kenney, R. W.; Khacheryan, S.; Kofler, R. R.; Langeveld, W. G. J.; Layter, J. G.; Lin, W. T.; Linde, F. L.; Loken, S. C.; Lu, A.; Lynch, G. R.; Madaras, R. J.; Magnuson, B. D.; Masek, G. E.; Mathis, L. G.; Matthews, J. A. J.; Maxfield, S. J.; Miller, E. S.; Moses, W.; Nygren, D. R.; Oddone, P. J.; Paar, H. P.; Park, S. K.; Pellett, D. E.; Pripstein, M.; Ronan, M. T.; Ross, R. R.; Rouse, F. R.; Schwitkis, K. A.; Sens, J. C.; Shapiro, G.; Shen, B. C.; Slater, W. E.; Smith, J. R.; Steinman, J. S.; Stephens, R. W.; Stevenson, M. L.; Stork, D. H.; Strauss, M. G.; Sullivan, M. K.; Takahashi, T.; Toutounchi, S.; Van Tyen, R.; Van Dalen, G. J.; Vernon, W.; Wagner, W.; Wang, E. M.; Wang, Y.-X.; Wenzel, W. A.; Wolf, Z. R.; Yamamoto, H.; Yellin, S. J.; Zeitlin, C.; TPC/Two-Gamma Collaboration

    1988-07-01

    We have observed formation of the f 1 (1285) in the reaction e +e -→e +e -π+π-η( η→ γγ). Its γγ ∗ width is determined in several Q2 bins. The γγ coupling parameter for the f 1 (1285) is found to be 2.4±0.5±0.5 keV. This value is compared to that for the X (1420), another J=1 state formed in γγ fusion reactions, which may belong to the same meson nonet.

  5. Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

    USGS Publications Warehouse

    Abrams, R.H.; Loague, K.; Kent, D.B.

    1998-01-01

    The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

  6. Effect of Ultrasonic Vibration on Unmixed Zone Formation

    SciTech Connect

    Cui, Yan; Xu, Cailu; Han, Qingyou

    2006-01-01

    Ultrasonic vibration was introduced into the molten super-austenitic-stainless weld metal during the shielded metal arc welding process. It was observed that the unmixed zone in the weld metal was completely eliminated by high-intensity ultrasonic vibrations. This is mainly due to a complete mixing of the molten filler metal and base metal, at the freezing front, caused by the acoustically induced cavitation and streaming. The elimination of the unmixed zone can significantly enhance the corrosion resistance of the weldment because the unmixed zone is the preferential location for the corrosion attack.

  7. Active zones of mammalian neuromuscular junctions: formation, density, and aging

    PubMed Central

    Nishimune, Hiroshi

    2012-01-01

    Presynaptic active zones are synaptic vesicle release sites that playessential roles in the function and pathology of mammalian neuromuscular junctions (NMJs). The molecular mechanisms of active zone organization utilize presynaptic voltage-dependent calcium channels (VDCCs) in NMJs as scaffolding proteins. VDCCs interact extracellularly with the muscle-derived synapse organizer, laminin β2, and interact intracellularly with active zone-specific proteins, such as Bassoon, CAST/Erc2/ELKS2alpha, ELKS, Piccolo, and RIMs. These molecular mechanisms are supported by studies in P/Q- and N-type VDCCs double-knockout mice, and they are consistent with the pathological conditions of Lambert-Eaton myasthenic syndrome and Pierson syndrome, which are caused by autoantibodies against VDCCs or by a laminin β2 mutation. During normal postnatal maturation, NMJs maintain the density of active zones, while NMJs triple their size. However, active zones become impaired during aging. Propitiously, muscle exercise ameliorates the active zone impairment in aged NMJs, which suggests the potential for therapeutic strategies. PMID:23252894

  8. The use of trace element zoning patterns in garnet to infer reaction paths of metamorphic rocks

    NASA Astrophysics Data System (ADS)

    Konrad-Schmolke, Matthias; Witte, Clemens; Dohmen, Ralf; O'Brien, Patrick; Erpel, Lars; Halama, Ralf; Schmidt, Alexander; Ditterova, Hana

    2015-04-01

    Garnet is one of the most versatile minerals in metamorphic petrology. It is stable over a large pressure and temperature range and thus occurs in many metamorphic environments. Garnet has a wide range of chemical compositions and its major and trace element composition well reflects the pressure (P), temperature (T) and chemical conditions (X) as well as the element transport kinetic properties of the host rock during growth. Hence, compositional growth zonations in garnet contain information about most geochemical, mineralogical and petrological properties of metamorphic rocks. However, detailed interpretation of complex zoning patterns in metamorphic garnet was hindered mainly by the lack of knowledge about the various contributions of kinetic and equilibrium effects to the trace element incorporation into garnet. In this contribution we combine thermodynamic equilibrium calculations together with mass balanced trace element distribution among coexisting phases with diffusion models that simulate kinetically controlled element transport in a reacting host rock. Comparison of the model results with natural garnets enables detailed interpretation of commonly observed major and trace element patterns in high-pressure (HP) and ultra-high pressure (UHP) garnets in terms of reaction paths and physico-chemical properties of the host rock. The comparison of our numerical models with a series of well-investigated (U)HP samples shows that the kinetic influence on rare earth element incorporation into garnet is limited in most rocks at the early stages of garnet growth and increases with increasing grade of rock transformation. We show that REE zoning patterns can be used to distinguish between cold (lawsonite-stable) and warm (epidote-stable) prograde reaction paths. REE liberation along a warm P-T trajectory occurs in three breakdown reactions involving chlorite, epidote and amphibole. All three reactions result in characteristic heavy (HREE) and medium (MREE) REE growth

  9. Formation of Complex Molecules via radiative association reactions

    NASA Astrophysics Data System (ADS)

    Acharyya, Kinsuk; Herbst, Eric

    2016-07-01

    The detection of increasing numbers of complex organic molecules in the various phases of star formation plays a key role since they follow the same chemical rules of carbon-based chemistry that are observed in our planet Earth. Many of these molecules are believed to be formed on the surfaces of grains, and can then be released to the gas phase when these grains are heated. This is evident when we observe a rich chemistry in hot core regions. However, recently complex organic molecules have also been observed in cold clouds. Therefore, it is necessary to re-examine various pathways for the formation of these molecules in the gas phase. In this presentation, I will discuss role of radiative association reactions in the formation of complex molecules in the gas phase and at low temperature. We will compare abundance of assorted molecules with and without new radiative association reactions and will show that the abundance of a few complex molecules such as HCOOCH3, CH3OCH3 etc. can go up due to introduction of these reactions, which can help to explain their observed abundances.

  10. Microkinetics of oxygenate formation in the Fischer-Tropsch reaction.

    PubMed

    van Santen, Rutger A; Ghouri, Minhaj; Hensen, Emiel M J

    2014-06-01

    Microkinetics simulations are presented on the intrinsic activity and selectivity of the Fischer-Tropsch reaction with respect to the formation of long chain oxygenated hydrocarbons. Two different chain growth mechanisms are compared: the carbide chain growth mechanism and the CO insertion chain growth mechanism. The microkinetics simulations are based on quantum-chemical data on reaction rate parameters of the elementary reaction steps of the Fischer-Tropsch reaction available in the literature. Because the overall rate constant of chain growth remains too low the CO insertion chain growth mechanism is not found to produce higher hydrocarbons, except for ethylene and acetaldehyde or the corresponding hydrogenated products. According to the carbide mechanism available quantum-chemical data are consistent with high selectivity to long chain oxygenated hydrocarbon production at low temperature. The anomalous initial increase with temperature of the chain growth parameter observed under such conditions is reproduced. It arises from the competition between the apparent rate of C-O bond activation to produce "CHx" monomers to be inserted into the growing hydrocarbon chain and the rate of chain growth termination. The microkinetics simulations data enable analysis of selectivity changes as a function of critical elementary reaction rates such as the rate of activation of the C-O bond of CO, the insertion rate of CO into the growing hydrocarbon chain or the rate constant of methane formation. Simulations show that changes in catalyst site reactivity affect elementary reaction steps differently. This has opposing consequences for oxygenate production selectivity, so an optimizing compromise has to be found. The simulation results are found to be consistent with most experimental data available today. It is concluded that Fischer-Tropsch type catalysis has limited scope to produce long chain oxygenates with high yield, but there is an opportunity to improve the yield of C2

  11. Method for selectively plugging highly permeable zones in a subterranean formation

    SciTech Connect

    Hoefner, M.L.

    1989-03-07

    A method for selectively plugging relatively high permeability zones in a subterranean formation having relatively high permeability zones and relatively low permeability zones penetrated by at least one injection well in fluid communication with a substantial portion of the formation comprising the sequential steps of: (a) injecting a predetermined amount of a solidifiable selective gel solution comprising xanthan chromium (in the 3+ state), sodium hydroxide and formaldehyde in a brine solution containing sodium chloride and calcium chloride into the formation via the injection well at a predetermined pressure sufficient to cause the gel solution to coat and temporarily plug the face of the relatively low permeability zones near the injection well without any significant amount of gel penetrating the relatively low permeability zones while allowing the gel solution to flow into the relatively high permeability zones; (b) thereafter injecting a predetermined amount of a solidifiable non-selective solution comprising polyacrylamides, polysaccharides and unpolymerized acrylamide monomers into the formation via the injection well before the previously injected selective gel solution solidifies in the relatively high permeability zones that preferentially enters the relatively high permeability zones and allowing the injected non-selective solution to solidify and plug the relatively high permeability zones; and (c) injecting a predetermined amount of a flushing agent having a gel breaker into the formation via the injection well that removes the selective gel coating from the face of the relatively low permeability zones thereby restoring permeability of the face of the relatively low permeability zones to fluids subsequently injected into the formation.

  12. Effect of reaction time on the formation of disinfection byproducts

    USGS Publications Warehouse

    Rathbun, R.E.

    1997-01-01

    The effect of reaction time on the trihalomethane and nonpurgeable total organic-halide formation potentials was determined by chlorinating water samples from the Mississippi, Missouri, and Ohio Rivers. Samples were collected for three seasons at 12 locations on the Mississippi from Minneapolis, Minnesota, to New Orleans, Louisiana, and on the Missouri and Ohio 1.6 kilometers above their confluences with the Mississippi. Both types of compounds formed rapidly during the initial stages of the reaction-time period, with formation rates decreasing with time. The ratio of the nonpurgeable total organic-halide and trihalomethane concentrations decreased with time, with the nonpurgeable total organic-halide compounds forming faster during the first stages of the time period and the trihalomethane compounds forming faster during the latter stages of the time period. Variation with distance along the Mississippi River of the formation rates approximately paralleled the variation of the dissolved organic carbon concentration, indicating that the rates of formation, as well as the concentrations of the compounds formed, depended on the dissolved organic carbon concentration.

  13. Acid-catalyzed Heterogeneous Reactions in SOA Formation

    NASA Astrophysics Data System (ADS)

    Ng, N.; Keywood, M.; Varutbangkul, V.; Gao, S.; Loewer, E.; Surratt, J.; Richard, F. C.; John, S. H.

    2003-12-01

    The importance of heterogeneous reactions in secondary organic aerosol (SOA) formation has recently excited a great deal of interest in the aerosol community. Jang and Kamens (2001) showed enhanced aerosol yield from aldehydes, which can be produced by atmospheric photochemical reactions, in the presence of acidic seed. They suggest that the carbonyl functional groups of the aldehydes further react in the aerosol phase via hydration, polymerization, and hemiacetal/acetal formation with alcohols at an accelerated rate in the presence of acid. Jang et al. (2003) demonstrated similar results using a flow reactor and Czoschke et al. (in press) qualitatively showed increased yields for isoprene and alpha-pinene ozonolysis in the presence of acidic seed. While these findings are intriguing and important, the conditions under which the experiments were carried out were atmospherically unrealistic. A series of SOA formation experiments have been carried out in the Caltech Indoor Chamber Facility, which is comprised of dual 28 m3 FEP Teflon chambers, with the flexibility to carry out both dark ozonolysis and photochemical OH oxidation reactions. Cycloheptene and alpha-pinene were oxidized in the presence of neutral seed under dry (<10% RH) and humid (50% RH) conditions and in the presence of acidic seed under humid (50% RH) conditions. The SOA yields for these experiments will be presented, and the extent of the influence of acid-catalyzed reactions on SOA yield will be discussed. Reference List 1. Cocker, D. R. III. and R. C. Flagan and J. H. Seinfeld, State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environmental Science and Technology, 35, 2594-2601, 2001. 2. Czoschke, N. M., M. Jang, and R. M. Kamens, Effect of acid seed on biogenic sceondary organic aerosol growth, Atmospheric Environment, In press. 3. Jang, M., S. Lee, and R. M. Kamens, Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor

  14. Exclusion-Zone Formation From Discontinuous Nafion Surfaces.

    PubMed

    Figueroa, Xavier A; Pollack, Gerald H

    2011-11-30

    Many hydrophilic materials in aqueous solution show near-surface zones that exclude suspended colloids and dissolved molecules. These exclusion zones (EZs) can extend for tens to hundreds of micrometers from the hydrophilic surface, and show physicochemical properties that differ from bulk water. So far, only continuous surfaces of polymers, gels, or biological specimens have been studied. In this report, we explore the interactions between exclusion zones generated by discontinuous, regularly spaced EZ-generating surfaces, namely strips of Nafion on a glass surface. Various inter-strip spacings were studied. When Nafion surfaces are separated by 100 micrometers or less, EZs merged with one another, forming a single, continuous, stable EZ. Separations larger than 100 micrometers produced discontinuous EZs that did not merge. This result has implication for the mechanism by which independent EZs can merge with one another. PMID:24826197

  15. Exclusion-Zone Formation From Discontinuous Nafion Surfaces

    PubMed Central

    Figueroa, Xavier A.; Pollack, Gerald H.

    2012-01-01

    Many hydrophilic materials in aqueous solution show near-surface zones that exclude suspended colloids and dissolved molecules. These exclusion zones (EZs) can extend for tens to hundreds of micrometers from the hydrophilic surface, and show physicochemical properties that differ from bulk water. So far, only continuous surfaces of polymers, gels, or biological specimens have been studied. In this report, we explore the interactions between exclusion zones generated by discontinuous, regularly spaced EZ-generating surfaces, namely strips of Nafion on a glass surface. Various inter-strip spacings were studied. When Nafion surfaces are separated by 100 micrometers or less, EZs merged with one another, forming a single, continuous, stable EZ. Separations larger than 100 micrometers produced discontinuous EZs that did not merge. This result has implication for the mechanism by which independent EZs can merge with one another. PMID:24826197

  16. Kinetics of enol formation from reaction of OH with propene.

    PubMed

    Huynh, Lam K; Zhang, Hongzhi R; Zhang, Shaowen; Eddings, Eric; Sarofim, Adel; Law, Matthew E; Westmoreland, Phillip R; Truong, Thanh N

    2009-04-01

    Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)/cc-pVDZ//B3LYP/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation (J. Phys. Chem. A 2006, 110, 10528). Of the two enol products, ethenol is dominant over propenol, and its pathway is also the dominant pathway for the OH + propene addition reactions to form bimolecular products. In the temperature range considered, hydrogen abstraction dominated propene + OH consumption by a branching ratio of more than 90%. Calculated rate constants of enol formation were included in the Utah Surrogate Mechanism to model the enol profile in a cyclohexane premixed flame. The extended model shows consistency with experimental data and gives 5% contribution of ethenol formation from OH + propene reaction, the rest coming from ethene + OH. PMID:19271758

  17. Compound nucleus formation in reactions between massive nuclei: Fusion barrier

    SciTech Connect

    Antonenko, N.V.; Cherepanov, E.A.; Nasirov, A.K.; Permjakov, V.P.; Volkov, V.V.

    1995-05-01

    The evaporation residue cross sections {sigma}{sub ER} in reactions between massive nuclei have been analyzed within different models of complete fusion. The calculations in the framework of the optical model, the surface friction model, and the macroscopic dynamic model can give the results which are by few orders of magnitude different from experimental data. This takes place due to neglect of the competition between complete fusion and quasifission. A possible mechanism of compound nucleus formation in heavy-ion-induced reactions has been suggested. The analysis of the complete fusion of nuclei on the basis of dinuclear system approach has allowed one to reveal an important feature of the fusion process of massive nuclei, that is, the appearance of the fusion barrier during dinuclear system evolution to a compound nucleus. As a result, the competition between complete fusion and quasifission arises and strongly reduces the cross section of the compound nucleus formation. A model is proposed for calculation of this competition in a massive symmetric dinuclear system. This model is applied for collision energies above the Coulomb barrier. The {sigma}{sub ER} values calculated in the framework of dinuclear system approach seem to be close to the experimental data. For illustration the reactions {sup 100}Mo+{sup 100}Mo, {sup 110}Pd+{sup 110}Pd, and {sup 124}Sn+{sup 96}Zr have been considered.

  18. Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

    NASA Astrophysics Data System (ADS)

    Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

    Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

  19. Formation of superheavy elements in cold fusion reactions

    NASA Astrophysics Data System (ADS)

    Smolańczuk, Robert

    2001-04-01

    We calculate the formation cross sections of transactinides (superheavy elements), as well as heavy actinides (No and Lr), which have been or might be obtained in fusion reactions with the evaporation of only one neutron. We use both more realistic fusion barrier and survival probability of the compound nucleus in comparison with the original phenomenological model [Phys. Rev. C 59, 2634 (1999)] that prompted the Berkeley experiment on the synthesis of a new superheavy element 118 [Phys. Rev. Lett. 83, 1104 (1999)]. Calculations are performed for asymmetric and symmetric target-projectile combinations and for reactions with stable and radioactive-ion beams. The formation cross sections measured at GSI-Darmstadt for transactinides and heavy actinides, as well as that for superheavy element 118 reported by the LBNL-Berkeley group, are reproduced within a factor of 2.4, on average. Based on the obtained relatively large cross sections, we predict that optimal reactions with stable beams for the synthesis of so far unobserved superheavy elements 119, 120, and 121 are 209Bi(86Kr, 1n)294119, 208Pb(88Sr, 1n)295120, and 209Bi(88Sr, 1n)296121, respectively. This is because of the magic of both the target and the projectile that leads to larger Q value and, consequently, lower effective fusion barrier with larger transmission probability. The same effect is responsible for relatively large cross sections predicted for the symmetric reactions 136Xe(124Sn, 1n)259Rf, 136Xe(136Xe, 1n)271Hs,138Ba(136Xe, 1n)273110, and 140Ce(136Xe, 1n)275112. Although shell effects in the magic nuclei 124Sn, 136Xe, 138Ba, and 140Ce are not as strong as in 208Pb and 209Bi, they act on both the target and the projectile and lead to the prediction of measurable cross sections.

  20. Hyporheic zone denitrification: Controls on effective reaction depth and contribution to whole-stream mass balance

    NASA Astrophysics Data System (ADS)

    Harvey, Judson W.; Böhlke, J. K.; Voytek, Mary A.; Scott, Durelle; Tobias, Craig R.

    2013-10-01

    Stream denitrification is thought to be enhanced by hyporheic transport but there is little direct evidence from the field. To investigate at a field site, we injected 15NO3-, Br (conservative tracer), and SF6 (gas exchange tracer) and compared measured whole-stream denitrification with in situ hyporheic denitrification in shallow and deeper flow paths of contrasting geomorphic units. Hyporheic denitrification accounted for between 1 and 200% of whole-stream denitrification. The reaction rate constant was positively related to hyporheic exchange rate (greater substrate delivery), concentrations of substrates DOC and nitrate, microbial denitrifier abundance (nirS), and measures of granular surface area and presence of anoxic microzones. The dimensionless product of the reaction rate constant and hyporheic residence time, λhzτhz define a Damköhler number, Daden-hz that was optimal in the subset of hyporheic flow paths where Daden-hz ≈ 1. Optimal conditions exclude inefficient deep pathways where substrates are used up and also exclude inefficient shallow pathways that require repeated hyporheic entries and exits to complete the reaction. The whole-stream reaction significance, Rs (dimensionless), was quantified by multiplying Daden-hz by the proportion of stream discharge passing through the hyporheic zone. Together these two dimensionless metrics, one flow-path scale and the other reach-scale, quantify the whole-stream significance of hyporheic denitrification. One consequence is that the effective zone of significant denitrification often differs from the full depth of the hyporheic zone, which is one reason why whole-stream denitrification rates have not previously been explained based on total hyporheic-zone metrics such as hyporheic-zone size or residence time.

  1. Hyporheic zone denitrification: controls on effective reaction depth and contribution to whole-stream mass balance

    USGS Publications Warehouse

    Harvey, Judson W.; Böhlke, John Karl; Voytek, Mary A.; Scott, Durelle; Tobias, Craig R.

    2013-01-01

    Stream denitrification is thought to be enhanced by hyporheic transport but there is little direct evidence from the field. To demonstrate at a field site, we injected 15NO3−, Br (conservative tracer), and SF6 (gas exchange tracer) and compared measured whole-stream denitrification with in situ hyporheic denitrification in shallow and deeper flow paths of contrasting geomorphic units. Hyporheic denitrification accounted for between 1 and 200% of whole-stream denitrification. The reaction rate constant was positively related to hyporheic exchange rate (greater substrate delivery), concentrations of substrates DOC and nitrate, microbial denitrifier abundance (nirS), and measures of granular surface area and presence of anoxic microzones. The dimensionless product of the reaction rate constant and hyporheic residence time, λhzτhz define a Damköhler number, Daden-hz that was optimal in the subset of hyporheic flow paths where Daden-hz ≈ 1. Optimal conditions exclude inefficient deep pathways transport where substrates are used up and also exclude inefficient shallow pathways that require repeated hyporheic entries and exits to complete the reaction. The whole-stream reaction significance, Rs (dimensionless), was quantified by multiplying Daden-hz by the proportion of stream discharge passing through the hyporheic zone. Together these two dimensionless metrics, one flow-path scale and the other reach-scale, quantify the whole-stream significance of hyporheic denitrification. One consequence is that the effective zone of significant denitrification often differs from the full depth of the hyporheic zone, which is one reason why whole-stream denitrification rates have not previously been explained based on total hyporheic-zone metrics such as hyporheic-zone size or residence time.

  2. The influence of metasomatic reactions on distributed vs. localized slip in ultramafic shear zones

    NASA Astrophysics Data System (ADS)

    Tarling, Matthew S.; Tulley, Chris J.; Smith, Steven A. F.

    2016-04-01

    The Livingstone Fault is a >1000 km long terrane boundary in New Zealand that juxtaposes ultramafic rocks of the Dun Mountain Ophiolite Belt against quartzofeldspathic rocks of the continental Caples Terrane. The fault is characterized by a zone of sheared serpentinite mélange tens to several hundreds of meters wide with a generally well-defined scaly fabric, containing entrained pods of massive serpentinite, volcanic rocks and quartzofeldspathic rocks. Talc- and tremolite- forming metasomatic reactions occurred frequently within the mélange zone, along the margins of the mélange and at the edges of entrained pods. These reactions were the result of the interaction between the serpentine minerals and silica bearing fluids derived from the quartzofeldspathic Caples Terrane. In the bulk of the mélange, structures such as distributed scaly fabrics, S-C fabrics, and networks of fibrous serpentine veins suggest a broad delocalization of strain, likely accommodated by pressure-solution mechanisms along the serpentinite- and talc-bearing fabrics. However, at the margins of the mélange zone and the edges of pods, layers of tremolite tens of centimeters thick are characterized by a highly indurated microstructure consisting of networks of tightly interwoven, acicular tremolite crystals forming a semi-nephritic to nephritic texture. In these metasomatic regions, discrete cataclastic slip zones associated with well-polished slickenlined surfaces are observed at the interfaces of the serpentinite and Caples Terrane quartzofeldspathics. In the Livingstone Fault, this style of highly-localized slip is uniquely associated withthe development of the indurated nephritic textures. Because tremolite is a frictionally-strong and generally velocity-weakening calc-silicate, we speculate that the tremolite-forming metasomatic reactions may have promoted localized and unstable fault slip within a shear zone that was otherwise deforming by creep. Employing scanning and transmission

  3. The effect of Co alloying content on the kinetics of reaction zone growth in tungsten fiber reinforced superalloy composites

    NASA Technical Reports Server (NTRS)

    Rodriguez, A.; Tien, J. K.; Caulfield, T.; Petrasek, D. W.

    1988-01-01

    A Co-free modified superalloy similar in composition to Waspaloy is investigated in an effort to understand the effect of Co on reaction zone growth kinetics and verify the chemistry dependence of reaction zone growth in the matrix of tungsten fiber reinforced superalloy composites. The values of the parabolic rate constant, characterizing the kinetics of reaction zone growth, for the Waspaloy matrix and the C-free alloy as well as five other alloys from a previous study confirm the dependence of reaction zone growth kinetics on cobalt content of the matrix. The Co-free alloy composite exhibits the slowest reaction zone growth among all tungsten fiber reinforced composites studied to date.

  4. Theoretical aspects of product formation from the NCO + NO reaction

    SciTech Connect

    Lin, M.C.; He, Y. ); Melius, C.F. )

    1993-09-09

    The reaction of NCO with NO, an important elementary process involved in the reduction of NO[sub x] by HNCO, has been studied theoretically using the BAC-MP4 technique in conjunction with RRKM calculations. The computed molecular structures and thermochemical data for various intermediates and transition states suggest that the reaction takes place primarily via the singlet, ground electronic state OCNNO molecule according to the following mechanism; (step a) NCO + NO [leftrightarrow] [sup 1]OCNNO [yields] N[sub 2]O + CO; (step b) NCO + NO [leftrightarrow] [sup 1]OCNNO [yields] c-OCNNO[minus] N[sub 2] + CO[sub 2]. The formation of N[sub 2]O + CO occurs by the fragmentation of the singlet OCNNO intermediate step (a), whereas the production of N[sub 2] + CO[sub 2] by cyclization-fragmentation occurs via step b. The tight transition states leading to the formation of these products, coupled with the loose entrance channel, give rise to the experimentally observed strong negative temperature dependence which can be quantitatively accounted for by the results of RRKM calculations based on the BAC-MP4 data. The experimentally measured product branching ratio for channels a and b could be accounted for theoretically by lowering the calculated energy barrier for step a by 3.6 kcal/mol, corresponding to about 15% of the barrier height. 22 refs., 3 figs., 5 tabs.

  5. Formation of molecular oxygen in ultracold O + OH reaction

    SciTech Connect

    Kendrick, Brian Kent; Quemener, Goulven; Balakrishman, Naduvalath

    2008-01-01

    We discuss the formation of molecular oxygen in ultracold collisions between hydroxyl radicals and atomic oxygen. A time-independent quantum formalism based on hyperspherical coordinates is employed for the calculations. Elastic, inelastic and reactive cross sections as well as the vibrational and rotational populations of the product O{sub 2} molecules are reported. A J-shifting approximation is used to compute the rate coefficients. At temperatures T = 10--100 mK for which the OH molecules have been cooled and trapped experimentally, the elastic and reactive rate coefficients are of comparable magnitude, while at colder temperatures, T < 1 mK, the formation of molecular oxygen becomes the dominant pathway. The validity of a classical capture model to describe cold collisions of OH and O is also discussed. While very good agreement is found between classical and quantum results at T = 0.3 K, at higher temperatures, the quantum calculations predict a higher rate coefficient than the classical model, in agreement with experimental data for the O + OH reaction. The zero-temperature limiting value of the rate coefficient is predicted to be about 6 x 10{sup -12} cm{sup 3} s{sup 01}, a value comparable to that of barrierless alkali metal atom-dimer systems and about a factor of five larger than that of the tunneling dominated F + H{sub 2} reaction.

  6. Experimental elaboration of faulting induced by fluid-releasing mineral reactions in subduction zones

    NASA Astrophysics Data System (ADS)

    Green, H.; Zhang, J.; Jung, H.; Dobrzinetskaya, L.

    2003-04-01

    Dehydration embrittlement has been cited repeatedly as a potential mechanism for triggering earthquakes at depths where unassisted brittle failure is impossible due to the normal-stress-dependence of friction. We are investigating two different aspects of this problem in the laboratory: (i) dehydration of antigorite under stress where the ΔV of reaction varies from strongly positive to distinctly negative; (ii) deformation of eclogite in which the nominally anhydrous minerals contain small amounts of dissolved H_2O that can lead to faulting induced by very small amounts of melting stimulated by exsolution of H_2O. (i) Antigorite has the largest stability field of the serpentines and is often cited as potentially being the source of most or all mantle earthquakes to a depth of over 200 km. However, like other low-pressure hydrous phases, the net volume change accompanying antigorite dehydration varies from strongly positive at low P to negative at P > ˜2-2.5 GPa. Fracture mechanics theory predicts that dehydration should not induce shear failure if ΔV<0. To test the effect of ΔV on faulting, we have deformed an extensively-serpentinized peridotite at P = 1-6 GPa. We conducted constant strain rate experiments in a Griggs-type apparatus at P = 1.0 - 3.4 GPa and rapid-pumping experiments in a Walker-type multianvil apparatus, culminating in pressures as high as 6 GPa. Independent of the sign of ΔV, specimens subjected to stress during dehydration yielded extremely thin zones of reaction products with shear offset across them. Some were clearly faults whereas others could be precursors to faulting. Fluid released at grain boundaries between antigorite and relict olivine locally produced Mode I cracks &fluid inclusions. (ii) Deformation of "wet" eclogite at 3 GPa and temperatures between the wet and dry solidi induced exsolution of H_2O and formation of very small amounts (<1%) of melt, leading to faulting. At lower temperature the rock was extremely strong but

  7. Monitoring of water and thermal transfers in the vadose zone of a carbonate reservoir formation.

    NASA Astrophysics Data System (ADS)

    Cerepi, A.; Loisy, C.; Burlot, R.

    2009-04-01

    The aim of this study is the monitoring of water and thermal transfers in vadose zone of a carbonate reservoir formation during three hydrological cycles (August 2001- November 2004). The application of the Time Domain Reflectometry (TDR) and Self-Potential (SP) methods to determine the water content of porous rock has been widely investigated. More than 285 studied point measurements of rock water content observed during three hydrological cycles and distributed among an abandoned underground quarry in Gironde, France, show a permanently undersaturated limestone (between 35% and 50 %). We also investigated the unsaturated zone in a borehole between 0 and 20 m depth until the water table. 14 TDR and SP electrodes investigate the vadose zone. For the understanding of the streaming potential and electric behaviour from the SP method of a vadose zone we performed an experimental device which allows us to quantify the measurements of electrokinetic coupling coefficient at various saturation conditions. The results show that the vadose zone is characterized by three different sub-zones which are different water dynamics. The shallow zone down to a depth of seven meters corresponds to a zone with a significant variation of water saturation related to evapotranspiration dynamic water. The second zone (so-called transition zone) between seven to sixteen meters displays a high stability. The third zone (zone of capillary fringe) between sixteen to twenty meter shows a high and constant water saturation. Experimental results show three periods of maximum water content corresponding to three occurring effective precipitations. The dephasing and the amplitude attenuation of the hydraulic and thermal waves with the depth can be modelled and explained by the physical properties of the porous medium in an unsaturated zone such as the diffusivity, the water relative permeability, the capillarity pressure versus water saturation and the effective porosity.

  8. Time scales for molecule formation by ion-molecule reactions

    NASA Technical Reports Server (NTRS)

    Langer, W. D.; Glassgold, A. E.

    1976-01-01

    Analytical solutions are obtained for nonlinear differential equations governing the time-dependence of molecular abundances in interstellar clouds. Three gas-phase reaction schemes are considered separately for the regions where each dominates. The particular case of CO, and closely related members of the Oh and CH families of molecules, is studied for given values of temperature, density, and the radiation field. Nonlinear effects and couplings with particular ions are found to be important. The time scales for CO formation range from 100,000 to a few million years, depending on the chemistry and regime. The time required for essentially complete conversion of C(+) to CO in the region where the H3(+) chemistry dominates is several million years. Because this time is longer than or comparable to dynamical time scales for dense interstellar clouds, steady-state abundances may not be observed in such clouds.

  9. Method for Controlling a Producing Zone of a Well in a Geological Formation

    NASA Technical Reports Server (NTRS)

    Arndt, G. Dickey (Inventor); Carl, James R. (Inventor); Byerly, Kent A. (Inventor); Amini, B. Jon (Inventor)

    2005-01-01

    System and methods for transmitting and receiving electromagnetic pulses through a geological formation. A preferably programmable transmitter having an all-digital portion in a preferred embodiment may be operated at frequencies below 1 MHz without loss of target resolution by transmitting and over sampling received long PN codes. A gated and stored portion of the received signal may be correlated with the PN code to determine distances of interfaces within the geological formation, such as the distance of a water interfaces from a wellbore. The received signal is oversampled preferably at rates such as five to fifty times as high as a carrier frequency. In one method of the invention, an oil well with multiple production zones may be kept in production by detecting an approaching water front in one of the production zones and shutting down that particular production zone thereby permitting the remaining production zones to continue operating.

  10. Method for controlling a producing zone of a well in a geological formation

    NASA Technical Reports Server (NTRS)

    Arndt, G. Dickey (Inventor); Carl, James R. (Inventor); Byerly, Kent A. (Inventor); Amini, B. Jon (Inventor)

    2005-01-01

    System and methods for transmitting and receiving electromagnetic pulses through a geological formation. A preferably programmable transmitter having an all-digital portion in a preferred embodiment may be operated at frequencies below 1 MHz without loss of target resolution by transmitting and over sampling received long PN codes. A gated and stored portion of the received signal may be correlated with the PN code to determine distances of interfaces within the geological formation, such as the distance of a water interfaces from a wellbore. The received signal is oversampled preferably at rates such as five to fifty times as high as a carrier frequency. In one method of the invention, an oil well with multiple production zones may be kept in production by detecting an approaching water front in one of the production zones and shutting down that particular production zone thereby permitting the remaining production zones to continue operating.

  11. Formation of Formaldehyde and Glyoxal From The Toluene + Oh Reaction

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Wirtz, K.; Platt, U.

    Aromatic hydrocarbons are emitted into the urban atmosphere mostly as part of au- tomobile exhaust. Toluene thereby is the single most abundant aromatic compound emitted into the atmosphere. Despite the importance of aromatic hydrocarbon oxi- dation for the formation of photooxidants from urban plumes the oxidation mech- anism of aromatic hydrocarbons is far from being understood.Considerable progress has been made in recent years concerning our understanding of the ring-retaining path- ways, while major uncertainties remain to be linked with the operative ring-cleavage mechanisms. The representation of the aromatic oxidation in presently used chemical transport models (CTM) is estimated a major uncertainty for these models. This work presents data on formaldehyde (HCHO) and glyoxal, which are two impor- tant ring-cleavage products from the the toluene + OH reaction. While glyoxal was observed to form as a high yield primary product (Volkamer et al., JPC A, 2001, 105, 7865-7874) the formation of HCHO is observed delayed, i.e. as a secondary prod- uct. The temporal behaviour of glyoxal and HCHO concentrations allowed to con- clude that short lived stable intermediate compounds must form upon ring-cleavage of toluene. With an approximate lifetime of the order of ten minutes, these highly reac- tive intermediate compounds are likely to be a significant radical source. Atmospheric implications of the results are adressed.

  12. The formation of Kuiper-belt binaries through exchange reactions.

    PubMed

    Funato, Yoko; Makino, Junichiro; Hut, Piet; Kokubo, Eiichiro; Kinoshita, Daisuke

    2004-02-01

    Recent observations have revealed that an unexpectedly high fraction--a few per cent--of the trans-Neptunian objects (TNOs) that inhabit the Kuiper belt are binaries. The components have roughly equal masses, with very eccentric orbits that are wider than a hundred times the radius of the primary. Standard theories of binary asteroid formation tend to produce close binaries with circular orbits, so two models have been proposed to explain the unique characteristics of the TNOs. Both models, however, require extreme assumptions regarding the size distribution of the TNOs. Here we report a mechanism that is capable of producing binary TNOs with the observed properties during the early stages of their formation and growth. The only required assumption is that the TNOs were initially formed through gravitational instabilities in the protoplanetary dust disk. The basis of the mechanism is an exchange reaction in which a binary whose primary component is much more massive than the secondary interacts with a third body, whose mass is comparable to that of the primary. The low-mass secondary component is ejected and replaced by the third body in a wide but eccentric orbit. PMID:14765188

  13. Preferential dealkylation reactions of s-triazine herbicides in the unsaturated zone

    USGS Publications Warehouse

    Mills, M.S.; Michael, Thurman E.

    1994-01-01

    The preferential dealkylation pathways of the s-triazine herbicides, atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), propazine [2-chloro-4,6-bis(isopropylamino)-s-triazine], and simazine [2-chloro-4,6-bis(ethylamino)-s-triazine], and two monodealkylated triazine metabolites, deisopropylatrazine (DIA: 2-amino-4-chloro-6-ethylamino-s-triazine) and deethylatrazine (DEA: 2-amino-4-chloro-6-isopropylamino-s-triazine) were investigated on two adjacent Eudora silt-loam plots growing corn (Zea mays L.). Results from the shallow unsaturated zone and surface-water runoff showed preferential removal of an ethyl side chain from atrazine, simazine, and DIA relative to an isopropyl side chain from atrazine, propazine, and DEA. It is hypothesized that deethylation reactions may proceed at 2-3 times the rate of deisopropylation reactions. It is concluded that small concentrations of DIA reportedly associated with the degradation of atrazine may be due to a rapid turnover rate of the metabolite in the unsaturated zone, not to small production levels. Because of continued dealkylation of both monodealkylated metabolites, a strong argument is advanced for the presence of a didealkylated metabolite in the unsaturated zone.

  14. PLANETESIMAL FORMATION IN MAGNETOROTATIONALLY DEAD ZONES: CRITICAL DEPENDENCE ON THE NET VERTICAL MAGNETIC FLUX

    SciTech Connect

    Okuzumi, Satoshi; Hirose, Shigenobu

    2012-07-01

    Turbulence driven by magnetorotational instability (MRI) affects planetesimal formation by inducing diffusion and collisional fragmentation of dust particles. We examine conditions preferred for planetesimal formation in MRI-inactive 'dead zones' using an analytic dead-zone model based on our recent resistive MHD simulations. We argue that successful planetesimal formation requires not only a sufficiently large dead zone (which can be produced by tiny dust grains) but also a sufficiently small net vertical magnetic flux (NVF). Although often ignored, the latter condition is indeed important since the NVF strength determines the saturation level of turbulence in MRI-active layers. We show that direct collisional formation of icy planetesimal across the fragmentation barrier is possible when the NVF strength is lower than 10 mG (for the minimum-mass solar nebula model). Formation of rocky planetesimals via the secular gravitational instability is also possible within a similar range of the NVF strength. Our results indicate that the fate of planet formation largely depends on how the NVF is radially transported in the initial disk formation and subsequent disk accretion processes.

  15. Migration of humus substances from soil to water and the main chemical reaction (in different natural zone of Russian Federation)

    NASA Astrophysics Data System (ADS)

    Dinu, Marina; Moiseenko, Tatiana; Gashkina, Natalia; Kremleva, Tatiana

    2014-05-01

    Migration of humus substances (HS) from soil to natural water has zonal specificity. Soil HS of different natural areas characterized by specific functional features, different molecular weight (MW) distribution and other physicochemical parameters. Due to the specifics of formation, waters in Russia widely distributed colored water with high concentrations of humus substances. HS involved in many chemical reactions in natural waters/soil. The most important: 1.Dissociation, association and same destruction - reactions are particularly important for assessing the acidification of natural waters 2.Complexation with metals - reactions reduce the toxicity of most metals We researched the differences in the qualitative and quantitative composition of soil HS catchment and HS in natural waters of some climatic zones. Samples were taking: the mixing zone forests (sod-podzolic soils) and the steppe zone (black earth) European Territory of Russia (ETR). In order to examine process of migration humus substances from soil to water have been performed HPLC, IR spectrometry and mass spectrometry analyses. We funded change of HS structure and MW in soil/water. The water HS of the mixed forest characterized as same ratio of functional groups as soil catchments. The molecular weight distribution in water - predominate medium (500-1000 kDa), and low molecular weight fractions (<100 kDa). HS water in steppe zone differs from catchment soils. In HS catchment soils predominate nitrogen- and sulfur- functional group and in HS water - nitrogen-, oxygen- functional group. The molecular weight of HS in natural waters is macromolecular fractions ( > 1000 kDa). For evaluating of the acidification effect on structures of humic substances in natural waters/soil we used date of survey more than 300 lakes on the European Russia (ETP) and Western Siberia (WS) for assessing chemical parameters. Chemical analyzes of water samples were performed by a single method in accordance with the

  16. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    PubMed

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E

    2014-12-16

    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated. PMID:25420634

  17. A "Fossil Vadose Zone" from the Triassic Cooper Canyon Formation (Dockum Group) of West Texas

    NASA Astrophysics Data System (ADS)

    Holt, R. M.; Hughes, E.; Hubbell, J. M.; Grisak, G.; Cook, S.; Pickens, J.; Griffith, B. C.

    2008-12-01

    Hydrogeologic investigations at a proposed low-level radioactive waste disposal facility in Andrews County, Texas, have revealed evidence of a "fossil vadose zone" present within the redbeds of the Cooper Canyon Formation. The Cooper Canyon Formation is the uppermost stratigraphic unit in the Triassic Dockum Group in the study area and consists of very low permeability claystone and mudstone with several areally extensive siltstone/sandstone interbeds. Piezometers installed within two of the siltstone/sandstone zones show that water levels can rise up to about 20 m above the top of the zones and that uppermost of these zones is locally unsaturated. Waters in these zones have radiometric age dates of about 16,000 years. Recently twelve boreholes were drilled into the Cooper Canyon, cored, and sampled for in situ water potential (the sum of the matric and osmotic potential) and other hydraulic properties including moisture content, porosity, electrical conductivity of a saturated paste (EC), and chloride content. Water potential and saturation data show that Cooper Canyon mudstones are unsaturated to depths greater than 110 m with water potentials typically ranging from -2 MPa to -5 MPa. Very low water potentials (less than -1 MPa) occur within 0.1 m to 1 m of the upper and lower contacts of the siltstone/sandstone zones. Hydraulic gradients are outward from the siltstone/sandstone zones, and water potential values in the mudstones show one or more minima. These conditions preclude vertical flow between the land surface and underlying units and between siltstone/sandstone zones. The average air-entry pressure for Cooper Canyon rocks is about -1 MPa, and water saturation averages 83%. Chloride concentration profiles show a strong bulge in the sediments and rocks above the Cooper Canyon suggesting that very little Holocene recharge has reached the redbeds. Chloride concentrations within the siltstone/sandstone zones are higher than the surrounding mudstones, indicating

  18. Time variation in the reaction-zone structure of two-phase spray detonations.

    NASA Technical Reports Server (NTRS)

    Pierce, T. H.; Nicholls, J. A.

    1973-01-01

    A detailed theoretical analysis of the time-varying detonation structure in a monodisperse spray is presented. The theory identifies experimentally observed reaction-zone overpressures as deriving from blast waves formed therein by the explosive ignition of the spray droplets, and follows in time the motion, change in strength, and interactions of these blast waves with one another, and with the leading shock. The results are compared with experimental data by modeling the motion of a finite-size circular pressure transducer through the theoretical data field in an x-t space.

  19. Reaction zone structure for strong, weak overdriven, and weak underdriven oblique detonations

    NASA Technical Reports Server (NTRS)

    Powers, Joseph M.; Gonthier, Keith A.

    1992-01-01

    A simple dynamic systems analysis is used to give examples of strong, weak overdriven, and weak underdriven oblique detonations. Steady oblique detonations consisting of a straight lead shock attached to a solid wedge followed by a resolved reaction zone structure are admitted as solutions to the reactive Euler equations. This is demonstrated for a fluid that is taken to be an inviscid, calorically perfect ideal gas that undergoes a two-step irreversible reaction with the first step exothermic and the second step endothermic. This model admits solutions for a continuum of shock wave angles for two classes of solutions identified by a Rankine-Hugoniot analysis: strong and weak overdriven waves. The other class, weak underdriven, is admitted for eigenvalue shock-wave angles. Chapman-Jouguet waves, however, are not admitted. These results contrast those for a corresponding onestep model that, for detonations with a straight lead shock, only admits strong, weak overdriven, and Chapman-Jouguet solutions.

  20. Modeling discrete gas bubble formation and mobilization during subsurface heating of contaminated zones

    NASA Astrophysics Data System (ADS)

    Krol, Magdalena M.; Mumford, Kevin G.; Johnson, Richard L.; Sleep, Brent E.

    2011-04-01

    During thermal remediation the increase in subsurface temperature can lead to bubble formation and mobilization. In order to investigate the effect of gas formation on resulting aqueous concentrations, a 2D finite difference flow and mass transport model was developed which incorporates a macroscopic invasion percolation (MIP) model to simulate bubble expansion and movement. The model was used to simulate three soil scenarios with different permeabilities and entry pressures at various operating temperatures and groundwater velocities. It was observed that discrete bubble formation occurred in all three soils, upward mobility being limited by lower temperatures and higher entry pressures. Bubble mobilization resulted in a different aqueous mass distribution than if no discrete gas formation was modeled, especially at higher temperatures. This was a result of bubbles moving upwards to cooler areas, then collapsing, and contaminating previously clean zones. The cooling effect also led to possible non-aqueous phase liquid (NAPL) formation which was not predicted using a model without discrete bubble formation.

  1. Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel; Decaris, Lionel

    2009-12-01

    We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the von Neumann spike and early part of the reaction zone make these measurements difficult. Here, we report results obtained from detonation experiments using VISAR (velocity interferometer system for any reflector) and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating nitromethane/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments. The experiments had either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation methods and the velocimetry systems were somewhat different. Some differences were observed in the peak particle velocity because of the ˜2 ns time resolution of the techniques—in all cases the peak was lower than the expected von Neumann spike. This is thought to be because the measurements were not high enough time resolution to resolve the spike.

  2. Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel

    2009-06-01

    We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the features (von Neumann spike and sonic locus) of the reaction zone make these measurements difficult. Here, we report results obtained from using and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating HE (nitromethane)/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments, in either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation systems and the velocimetry systems were different. Some differences were observed in the von Neumann spike height because of the approximately 2 nanosecond time resolution of the techniques -- in some or all cases the spike top was truncated.

  3. The Gaseous Explosive Reaction : the Effect of Pressure on the Rate of Propagation of the Reaction Zone and upon the Rate of Molecular Transformation

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1932-01-01

    This study of gaseous explosive reaction has brought out a number of important fundamental characteristics of the explosive reaction indicating that the basal processes of the transformation are much simpler and corresponds more closely to the general laws and principles of ordinary transformations than is usually supposed. The report calls attention to the point that the rate of molecular transformation within the zone was found in all cases to be proportional to pressure, that the transformation within the zone is the result of binary impacts. This result is of unusual interest in the case of the reaction of heavy hydrocarbon fuels and the reaction mechanism proposed by the recent kinetic theory of chain reactions.

  4. Poly(dimethylsiloxane) microchip-based immunoassay with multiple reaction zones: Toward on-chip multiplex detection platform

    SciTech Connect

    Shao, Guocheng; Wang, Jun; Li, Zhaohui; Saraf, Laxmikant V.; Wang, Wanjun; Lin, Yuehe

    2011-09-20

    In this work, a poly(dimethylsiloxane) (PDMS) microchip-based immuno-sensing platform with integrated pneumatic micro valves is described. The microchip was fabricated with multiple layer soft lithography technology. By controlling the activation status of corresponding valves, reagent flows in the microchannel network can be well manipulated so that immuno-reactions only take place at designated reaction zones (DRZs). Four DRZs are included in the prototype microchip. Since these DRZs are all isolated from each other by micro valves, cross contamination is prevented. Using the inner surface of the all-PDMS microchannel as immunoassay substrate, on-chip sandwich format solid phase immunoassay was performed to demonstrate the feasibility of this immuno-sensing platform. Mouse IgG and fluorescein isothiocyanate (FITC) were used as the model analyte and the signal reporter respectively. Only 10 ul sample is needed for the assay and low detection limit of 5 ng/ml (≈33 pM) was achieved though low-cost polyclonal antibodies were used in our experiment for feasibility study only. The encouraging results from mouse IgG immunoassay proved the feasibility of our microchip design. With slight modification of the assay protocol, the same chip design can be used for multi-target detection and can provide a simple, cost-effective and integrated microchip solution for multiplex immunoassay applications.

  5. Origin and formation of carbonaceous material veins in the 2008 Wenchuan earthquake fault zone

    NASA Astrophysics Data System (ADS)

    Liu, Jiang; Li, Haibing; Zhang, Jinjiang; Zhang, Bo

    2016-02-01

    This paper establishes a reference data set of carbonaceous materials (CMs) from the active fault zone of the Longmen Shan fault belt that ruptured in the 2008 Mw7.9 Wenchuan earthquake and presents an application of these data for studies of both other exhumed carbonaceous-rich fault zones and deep-drilling cores. The CMs distributed in the active fault zone are found as narrow veins and located along the slip surfaces. Microstructural observation shows that the carbonaceous material veins (CMVs) are located along slip surfaces in the fault gouge zones. Some CMVs have a cataclastic fabric, and their branches intrude into voids around the slip surfaces. Raman spectra of the CMVs show a wide (full width at half maximum >200 cm-1) D-peak at ~1345 cm-1 (defect peak), which is much lower than the O-peak at ~1595 cm-1 (ordered peak), indicating a metamorphic temperature of zeolite facies or lower than 250 °C. In addition, the stable carbon isotopic compositions (δ13C values) of the CMVs, ranging from -23.4 to -26.4‰, are very similar to that of the kerogen collected from the Late Triassic Xujiahe Formation in Sichuan Basin. Given the data at which it may be formed, the Xujiahe Formation is the most likely origin of CMs for the CMVs, and it seems that some CMVs in the fault zone were crushed and intruded into the voids during coseismic events, possibly driven by an enhanced pore fluid pressure. Since graphitization is suggested as an indicator of transient frictional heating in this area, our study providing a reference data set of CMs would help future CM-rich fault-zone research to retrieve seismic signatures presumably occurring in the Longmen Shan fault zone belt.

  6. Structural analysis of high-pressure shear zones (Bacariza Formation, Cabo Ortegal, NW Spain)

    NASA Astrophysics Data System (ADS)

    Puelles, P.; Mulchrone, K. F.; Ábalos, B.; Ibarguchi, J. I. Gil

    2005-06-01

    High-pressure granulites of the Bacariza Formation (Cabo Ortegal Complex, NW Spain) exhibit spectacular examples of ductile shear zones developed at different scales in rocks containing pre-existing foliations. A detailed structural analysis was carried out on these shear zones in order to unravel and compare the role of various parameters controlling the deformation process (i.e. heterogeneous simple shear, components of homogeneous deformation, heterogeneous volume change and degree of non-coaxiality). Although heterogeneous simple shear largely dominated, negligible deviations from the ideal simple shear model were detected involving shortening along the structural directions perpendicular to the stretching axis (within the foliation plane) of the finite strain ellipsoid. The relationship between displacement parallel to a half-shear zone and the normal distance from its boundary provided the basis for the estimation of the stress exponent in the power-law constitutive flow equation associated with each shear zone, which is interpreted as a rheological indicator. These geometric and rheological results, and the thermobaric conditions of high-pressure shear zone deformation, indicate that these shear zones accommodated dominant plastic rock flow coeval with high-pressure and high-temperature deformations under moderate stress levels concomitant with elevated strain rates.

  7. Reducing permeability of highly permeable zones in oil and gas formations

    SciTech Connect

    Allison, J.D.

    1988-09-27

    This patent describes a process for reducing flow into a thief zone penetrated by a water injection well bore which comprises injecting down the well bore and into the thief zone a mixture of an aqueous solution of a water soluble polyalkylenimine polymer and a cross-linking agent containing difunctional groups which are capable of delayed cross-linking with the polymer whereby delayed indepth gelling of the polymer takes place in the formation, the cross-linking agent being selected from the group consisting of difunctional aldehydes, ketones, alkyl halides, isocyanates, carboxylic acids and compounds having activated double bonds.

  8. Formation of the compression zone in a plasma flow generated by a magnetoplasma compressor

    SciTech Connect

    Solyakov, D. G. Petrov, Yu. V.; Garkusha, I. E.; Chebotarev, V. V.; Ladygina, M. S.; Cherednichenko, T. N.; Morgal’, Ya. I.; Kulik, N. V.; Stal’tsov, V. V.; Eliseev, D. V.

    2013-12-15

    Processes occurring in a plasma flow generated by a magnetoplasma compressor (MPC) during the formation of the compression zone are discussed. The paper presents results of measurements of the spatial distribution of the electric current in the plasma flow, the temporal and spatial (along the flow) distributions of the plasma density, and the profiles of the velocity of individual flow layers along the system axis. The spatial distribution of the electromagnetic force in the flow is analyzed. It is shown that the plasma flow is decelerated when approaching the compression zone and reaccelerated after passing it. In this case, the plasma flow velocity decreases from ν = (2–3) × 10{sup 7} cm/s at the MPC output to ν < 10{sup 6} cm/s in the region of maximum compression and then again increases to 10{sup 7} cm/s at a distance of 15–17 cm from the MPC output. In some MPC operating modes, a displacement of the magnetic field from the compression zone and the formation of toroidal electric current vortices in the plasma flow after passing the compression zone were detected.

  9. Experimental and Thermokinetic Simulation Studies on the Formation of Deleterious Zones in Dissimilar Ferritic Steel Weldments

    NASA Astrophysics Data System (ADS)

    Anand, R.; Sudha, C.; Saroja, S.; Vijayalakshmi, M.

    2013-05-01

    The methods to predict and prevent the formation of hard and soft zones in dissimilar weldments of 9Cr-1Mo and 2¼Cr-1Mo ferritic steels during high-temperature exposure are examined in this article. The computational studies have been carried out using multicomponent diffusion model incorporated in Dictra and validated by experimental methods using EPMA and TEM. Carbon concentration profiles across the interface of the weld joint between the two ferritic steels were simulated in the temperatures ranging from 823 K to 1023 K (from 550 °C to 750 °C) for various time durations using "diffusion in dispersed phase model" in Dictra. When precipitation and diffusion were incorporated into the calculations simultaneously, the agreement was better between the calculated and the experimentally measured values of carbon concentration profiles, type, and volume fractions of carbides in the hard zone and diffusion zone, width, and the activation energy. Calculation results of thermodynamic potentials of carbon in 2¼Cr-1Mo and 9Cr-1Mo steels suggested that the diffusion is driven by the activity gradient of carbon across the joint. The effectiveness of nickel-based diffusion barrier in suppressing the formation of hard and soft zones is demonstrated using calculations based on the cell model incorporated in Dictra.

  10. Reaction Weakening of Dunite in Friction Experiments at Hydrothermal Conditions and Its Relevance to Subduction Zones

    NASA Astrophysics Data System (ADS)

    Moore, D. E.; Lockner, D. A.

    2014-12-01

    To improve our understanding of processes occurring in the mantle wedge near the downdip limit of seismicity in subduction zones, we conducted triaxial friction tests on dunite gouge at temperatures in the range 200-350°C, 50 MPa fluid pressure and 100 MPa effective normal stress. Dunite, quartzite, and granite forcing blocks were used respectively to approximate changing rock/fluid chemistry with decreasing distance above the subduction thrust. All experiments were characterized by an initial increase in frictional strength to a peak value, followed by a decrease associated with shearing-enhanced alteration of the dunite gouge. Reaction products and the extent of weakening varied with the chemical environment. In the dunite-block experiments, strength gradually declined from the peak value to a coefficient of friction, µ ~ 0.5-0.6, consistent with the frictional strength of serpentine that formed on the shear surfaces from alteration of the gouge. Interaction of dunite gouge with quartzite and granite driving blocks resulted in significantly greater weakening, to μ ~ 0.3, at temperatures of 250°C and higher. Talc and serpentine partly replaced dunite gouge sheared between quartzite blocks, and metastable saponitic smectite clays crystallized in dunite sheared between granite blocks, as a result of fluid-assisted chemical exchange with the minerals in the wall rocks. These results suggest that rapid and substantial weakening can occur in the mantle wedge immediately overlying the subducting slab. Whichever the chemical environment, attainment of peak strength typically was accompanied by oscillatory slip with small stress drops that gradually was replaced by stable slip with increasing displacement. This oscillatory behavior in some ways resembles the tremor events that have been reported near the forearc mantle corner in subduction zones, and it may indicate the possible involvement of mineral reactions in some instances of tremor.

  11. Modelling the Formation of Liver Zones within the Scope of Fractional Order Derivative

    PubMed Central

    Atangana, Abdon; Oukouomi Noutchie, Suares Clovis

    2014-01-01

    We develop and extend earlier results related to mathematical modelling of the liver formation zone by the adoption of noninteger order derivative. The hidden uncertainties in the model are captured and controlled thanks to the Caputo derivative. The stationary states are investigated and the time-dependent solution is approximated using two recent iteration methods. In particular, we discuss the convergence of these methods by constructing a suitable Hilbert space. PMID:25276791

  12. Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates.

    PubMed

    Roca-López, David; Polo, Victor; Tejero, Tomás; Merino, Pedro

    2015-04-17

    The mechanism of the reaction between nitrones and lithium ynolates has been studied using DFT methods at the M06-2X/cc-pVTZ/PCM=THF level. After the formation of a starting complex an without energy barrier, in which the lithium atom is coordinated to both nitrone and ynolate, the reaction takes place in one single kinetic step through a single transition structure. However, the formation of C-C and C-O bonds takes place sequentially through a typical two-stage, one-step process. A combined study of noncovalent interactions (NCIs) and electron localization function (ELFs) of selected points along the intrinsic reaction coordinate (IRC) of the reaction confirmed that, in the transition structure, only the C-C bond is being formed to some extent, whereas an electrostatic interaction is present between carbon and oxygen atoms previous to the formation of the C-O bond. Indeed, the formation of the second C-O bond only begins when the first C-C bond is completely formed without formation of any intermediate. Once the C-C bond is formed and before the C-O bond formation starts the RMS gradient norm dips, approaching but not reaching 0, giving rise to a hidden intermediate. PMID:25803829

  13. Gas-oil fluids in the formation of travertines in the Baikal rift zone

    NASA Astrophysics Data System (ADS)

    Tatarinov, A. A.; Yalovik, L. I.; Shumilova, T. G.; Kanakin, S. V.

    2016-07-01

    Active participation of gas-oil fluids in the processes of mineral formation and petrogenesis in travertines of the Arshan and Garga hot springs is substantiated. The parageneses of the products of pyrolytic decomposition and oxidation of the gas-oil components of hydrothermal fluids (amorphous bitumen, graphite-like CM, and graphite) with different genetic groups of minerals crystallized in a wide range of P-T conditions were established. Travertines of the Baikal rift zone were formed from multicomponent hydrous-gas-oil fluids by the following basic mechanisms of mineral formation: chemogenic, biogenic, cavitation, fluid pyrometamorphism, and pyrolysis.

  14. Dienamine-Catalyzed Nitrone Formation via Redox Reaction.

    PubMed

    Fraboni, Americo J; Brenner-Moyer, Stacey E

    2016-05-01

    The first catalytic method to directly introduce nitrone functionality onto aldehyde substrates is described. This reaction proceeds by an unprecedented organocatalytic redox mechanism in which an enal is oxidized to the γ-nitrone via dienamine catalysis, thereby reducing an equivalent of nitrosobenzene. This reaction is a unique example of divergent reactivity of an enal, which represents a novel strategy for rapidly accessing small libraries of N,O-heterocycles. Alternatively, divergent reactivity can be suppressed simply by changing solvents. PMID:27070296

  15. Pattern Formation and Reaction Textures during Dunite Carbonation

    NASA Astrophysics Data System (ADS)

    Lisabeth, H. P.; Zhu, W.

    2015-12-01

    Alteration of olivine-bearing rocks by fluids is one of the most pervasive geochemical processes on the surface of the Earth. Serpentinized and/or carbonated ultramafic rocks often exhibit characteristic textures on many scales, from polygonal mesh textures on the grain-scale to onion-skin or kernel patterns on the outcrop scale. Strong disequilibrium between pristine ultramafic rocks and common geological fluids such as water and carbon dioxide leads to rapid reactions and coupled mechanical and chemical feedbacks that manifest as characteristic textures. Textural evolution during metasomatic reactions can control effective reaction rates by modulating dynamic porosity and therefore reactant supply and reactive surface area. We run hydrostatic experiments on thermally cracked dunites saturated with carbon dioxide bearing brine at 15 MPa confining pressure and 150°C to explore the evolution of physical properties and reaction textures as carbon mineralization takes place in the sample. Compaction and permeability reduction are observed throughout experiments. Rates of porosity and permeability changes are sensitive to pore fluid chemistry. After reaction, samples are imaged in 3-dimension (3D) using a dual-beam FIB-SEM. Analysis of the high resolution 3D microstructure shows that permeable, highly porous domains are created by olivine dissolution at a characteristic distance from pre-existing crack surfaces while precipitation of secondary minerals such as serpentine and magnesite is limited largely to the primary void space. The porous dissolution channels provide an avenue for fluid ingress, allow reactions to continue and could lead to progressive hierarchical fracturing. Initial modeling of the system indicates that this texture is the result of coupling between dissolution-precipitation reactions and the local stress state of the sample.

  16. Quantum chemical mechanism in parasitic reaction of AlGaN alloys formation

    NASA Astrophysics Data System (ADS)

    Makino, Osamu; Nakamura, Koichi; Tachibana, Akitomo; Tokunaga, Hiroki; Akutsu, Nakao; Matsumoto, Koh

    2000-06-01

    The mechanism of parasitic reactions among trimethylaluminum (TMA), trimethylgallium (TMG), and NH 3 in atmospheric pressure (AP) MOVPE for growth of AlGaN is theoretically studied using the quantum chemical method. The calculations show that metal-nitrogen chain growth reaction easily proceeds through the successive reactions of 'complex formation with NH 3' and 'CH 4 elimination by the bimolecular mechanism'. Additionally, a parasitic reaction in APMOVPE using other raw material is also investigated. The calculated result shows that small change of raw material raises activation energy of parasitic reaction, and, thus, the parasitic reaction is suppressed. This result suggests a way to improve APMOVPE by a suitable choice of substituent.

  17. An Investigation of Model Catalyzed Hydrocarbon Formation Reactions

    SciTech Connect

    Tysoe, W. T.

    2001-05-02

    Work was focused on two areas aimed at understanding the chemistry of realistic catalytic systems: (1) The synthesis and characterization of model supported olefin metathesis catalysts. (2) Understanding the role of the carbonaceous layer present on Pd(111) single crystal model catalysts during reaction.

  18. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969. As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: that is machine-readable (for checking and indicating possible errors); that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  19. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  20. Brittle-ductile shear zone formation in the McKim Limestone: eastern Monument Upwarp, Utah

    NASA Astrophysics Data System (ADS)

    Seyum, S.; Pollard, D. D.

    2011-12-01

    The McKim Limestone is part of a regressive, marine sedimentary sequence of strata that was deposited in the Pennsylvanian to Permian periods. It is well-exposed across large portions of Raplee anticline and Comb monocline; a pair of kilometer-scale folds that mark the Monument Upwarp of the Colorado Plateau in southeastern Utah. Two conjugate sets of echelon vein arrays, with complementary echelon pressure solution seam arrays, occur as bed-perpendicular, systematic deformation features in the 1-3 m thick McKim Limestone unit. Based on large vein to vein array angles, large vein aperture to length ratios, and the presence of vein-perpendicular pressure solution seams, these structures are interpreted to have developed within localized, brittle-ductile shear zones. Topics of debate among structural geologists regarding the formation mechanism of echelon veins include the initiation mode of vein segments (tensile or shear), the relative age between shear zone initiation and vein formation, the interpretation of strain within a shear zone, and the development of sigmoidal veins as being indicative of rotation. These concepts often are founded on geometric observations and kinematic models of deformation (e.g. simple shear) that are independent of the constitutive properties of the rock, are not constrained by the equations of motion, and do not honor the boundary conditions on the vein surfaces. Here we show a more realistic representation of brittle-ductile shear zone formation by introducing numerical models that consider the mechanical properties of limestone, are constrained by the equations of motion, and explicitly define the vein surfaces and their boundary conditions. The commercial finite element software, Abaqus FEA, is used to investigate the deformed geometry of model echelon vein arrays as a function of the remotely applied stress, the initial geometry of the vein arrays, and the constitutive properties of the solid. These geometric patterns are compared

  1. Predicting brittle zones in the Bakken Formation using well logs and seismic data

    NASA Astrophysics Data System (ADS)

    Beecher, Michael E.

    The oil-in-place estimate for the Bakken Formation has varied from 10 billion barrels in 1974 to 503 billion barrels in 1999. However, only a small fraction of this estimate is recoverable due to the formation having very low porosity and permeability. Implementation of hydraulic fracture stages along horizontal wells in the Bakken has been productive. Recently, identification of zones where the formation is brittle has been used to improve hydraulic fracture stimulation efficiency in an effort to improve production. The first goal for this thesis is to identify a correlation between brittleness and production data by using elastic moduli and normalized production values. The hypothesis for this study is that rock with a low Poisson's ratio and high Young's modulus will be more brittle and will ultimately produce a higher amount of oil than more ductile rock. The next goal was to create and test a method to identify brittle zones with high normalized production in a 3D seismic data set without well control using producing wells from outside the survey with dipole sonic logs from the Bakken Formation. Correlations between normalized production values and elastic moduli were subsequently identified. Cumulative first-four-months' production was found to have the best correlation to the elastic moduli. Correlations of normalized production values and Poisson's ratio showed that sections of the middle Bakken with low Poisson's ratio yield higher normalized production values. Correlations of Young's modulus and normalized production showed that middle Bakken zones with low Young's modulus have higher normalized production values. However, when using additional wells that were not used for well-to-3D seismic correlations, the correlation shows that higher Young's modulus yield higher normalized production. The correlation with additional wells best represented the data and agrees with the initial hypothesis. Brittle zones were mapped in a 3D seismic data set by

  2. Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport

    USGS Publications Warehouse

    Molins, S.; Mayer, K.U.; Amos, R.T.; Bekins, B.A.

    2010-01-01

    Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O2, and the release of CH4 and CO2 from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O2, CH4, and CO2) and non-reactive (Ar and N2) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH4 concentrations. In accordance with field observations, zones of volatilization and CH4 generation are correlated to slightly elevated total gas pressures and low partial pressures of N2 and Ar, while zones of aerobic CH4 oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N2 and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH4, and to a more limited extent to O2 ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions and vadose zone carbon

  3. Coupled transport and reaction kinetics control the nitrate source-sink function of hyporheic zones

    NASA Astrophysics Data System (ADS)

    Zarnetske, Jay P.; Haggerty, Roy; Wondzell, Steven M.; Bokil, Vrushali A.; GonzáLez-Pinzón, Ricardo

    2012-11-01

    The fate of biologically available nitrogen (N) and carbon (C) in stream ecosystems is controlled by the coupling of physical transport and biogeochemical reaction kinetics. However, determining the relative role of physical and biogeochemical controls at different temporal and spatial scales is difficult. The hyporheic zone (HZ), where groundwater-stream water mix, can be an important location controlling N and C transformations because it creates strong gradients in both the physical and biogeochemical conditions that control redox biogeochemistry. We evaluated the coupling of physical transport and biogeochemical redox reactions by linking an advection, dispersion, and residence time model with a multiple Monod kinetics model simulating the concentrations of oxygen (O2), ammonium (NH4), nitrate (NO3), and dissolved organic carbon (DOC). We used global Monte Carlo sensitivity analyses with a nondimensional form of the model to examine coupled nitrification-denitrification dynamics across many scales of transport and reaction conditions. Results demonstrated that the residence time of water in the HZ and the uptake rate of O2 from either respiration and/or nitrification determined whether the HZ was a source or a sink of NO3 to the stream. We further show that whether the HZ is a net NO3 source or net NO3 sink is determined by the ratio of the characteristic transport time to the characteristic reaction time of O2 (i.e., the Damköhler number, DaO2), where HZs with DaO2 < 1 will be net nitrification environments and HZs with DaO2 ≪ 1 will be net denitrification environments. Our coupling of the hydrologic and biogeochemical limitations of N transformations across different temporal and spatial scales within the HZ allows us to explain the widely contrasting results of previous investigations of HZ N dynamics which variously identify the HZ as either a net source or sink of NO3. Our model results suggest that only estimates of residence times and O2uptake rates

  4. Chronostratigraphic significance of cathodoluminescence zoning in syntaxial cement: Mississippian Lake Valley Formation, New Mexico

    NASA Astrophysics Data System (ADS)

    Frank, Tracy D.; Lohmann, Kyger C.; Meyers, William J.

    1996-08-01

    Echinoderm-syntax ial cement crystals have been collected at several stratigraphic levels within the Lake Valley Formation, which is overlain by a major pre-Pennsylvanian subaerial exposure surface. The crystals were microsampled along growth bands, and yielded high-resolution elemental and isotopic information that record fluid evolution during their growth. Although cement crystals show little variation in cathodoluminescence character and bulk chemistry throughout the regional extent of the formation, intracrystalline patterns in minor element and stable isotope chemistry allow for the identification of several settings of cementation, including the marine phreatic, marine-meteoric mixing, and meteoric phreatic zones. When placed in a regional-stratigraphic context, crystal growth records enable reconstruction of the temporal and spatial extent of these diagenetic environments. Isotopic, petrographic and stratigraphic constraints indicate that cementation was related to two temporally distinct meteoric systems. Most Lake Valley Formation syntaxial cement formed in the marine phreatic and marine-meteoric mixing zones during the earliest phase of cementation. Of this cement, in excess of 60% formed in the marine phreatic zone and lowermost marine-meteoric mixing zone. Smaller volumes precipitated from progressively fresher mixtures of marine and meteoric fluid during the gradual expansion of a freshwater lens that developed in response to pre-Pennsylvanian lowering of sea level. Meteoric phreatic fluids were relatively unimportant during this episode of cementation. In contrast, cement of entirely meteoric phreatic origin is associated with a later meteoric system, but is found only in the northern part of the study area and at stratigraphic levels immediately adjacent to the pre-Pennsylvanian unconforrnity. Our results indicate that cements in the upper and lower parts of the Lake Valley Formation are genetically and temporally unrelated. Thus, the cement

  5. Periodic stripe formation by a Turing-mechanism operating at growth zones in the mammalian palate

    PubMed Central

    Economou, Andrew D.; Ohazama, Atsushi; Porntaveetus, Thantrira; Sharpe, Paul T.; Kondo, Shigeru; Basson, M. Albert; Gritli-Linde, Amel; Cobourne, Martyn T.; Green, Jeremy B.A.

    2012-01-01

    We present direct evidence of an activator-inhibitor system in the generation of the regularly spaced transverse ridges of the palate. We show that new ridges, or rugae, marked by stripes of Sonic hedgehog (Shh) expression, appear at two growth zones where the space between previously laid-down rugae increases. However, inter-rugal growth is not absolutely required: new stripes still appear when growth is inhibited. Furthermore, when a ruga is excised new Shh expression appears, not at the cut edge but as bifurcating stripes branching from the neighbouring Shh stripe, diagnostic of a Turing-type reaction-diffusion mechanism. Genetic and inhibitor experiments identify Fibroblast Growth Factor (FGF) and Shh as an activator-inhibitor pair in this system. These findings demonstrate a reaction-diffusion mechanism likely to be widely relevant in vertebrate development. PMID:22344222

  6. Heterotrimeric kinesin-2 (KIF3) mediates transition zone and axoneme formation of mouse photoreceptors.

    PubMed

    Jiang, Li; Wei, Yuxiao; Ronquillo, Cecinio C; Marc, Robert E; Yoder, Bradley K; Frederick, Jeanne M; Baehr, Wolfgang

    2015-05-15

    Anterograde intraflagellar transport (IFT) employing kinesin-2 molecular motors has been implicated in trafficking of photoreceptor outer segment proteins. We generated embryonic retina-specific (prefix "emb") and adult tamoxifen-induced (prefix "tam") deletions of KIF3a and IFT88 in adult mice to study photoreceptor ciliogenesis and protein trafficking. In (emb)Kif3a(-/-) and in (emb)Ift88(-/-) mice, basal bodies failed to extend transition zones (connecting cilia) with outer segments, and visual pigments mistrafficked. In contrast, (tam)Kif3a(-/-) and (tam)Ift88(-/-) photoreceptor axonemes disintegrated slowly post-induction, starting distally, but rhodopsin and cone pigments trafficked normally for more than 2 weeks, a time interval during which the outer segment is completely renewed. The results demonstrate that visual pigments transport to the retinal outer segment despite removal of KIF3 and IFT88, and KIF3-mediated anterograde IFT is responsible for photoreceptor transition zone and axoneme formation. PMID:25825494

  7. Interploidy hybridization in sympatric zones: the formation of Epidendrum fulgens × E. puniceoluteum hybrids (Epidendroideae, Orchidaceae)

    PubMed Central

    Moraes, Ana P; Chinaglia, Mariana; Palma-Silva, Clarisse; Pinheiro, Fábio

    2013-01-01

    Interspecific hybridization is a primary cause of extensive morphological and chromosomal variation and plays an important role in plant species diversification. However, the role of interploidal hybridization in the formation of hybrid swarms is less clear. Epidendrum encompasses wide variation in chromosome number and lacks strong premating barriers, making the genus a good model for clarifying the role of chromosomes in postzygotic barriers in interploidal hybrids. In this sense, hybrids from the interploidal sympatric zone between E. fulgens (2n = 2x = 24) and E. puniceoluteum (2n = 4x = 56) were analyzed using cytogenetic techniques to elucidate the formation and establishment of interploidal hybrids. Hybrids were not a uniform group: two chromosome numbers were observed, with the variation being a consequence of severe hybrid meiotic abnormalities and backcrossing with E. puniceoluteum. The hybrids were triploids (2n = 3x = 38 and 40) and despite the occurrence of enormous meiotic problems associated with triploidy, the hybrids were able to backcross, producing successful hybrid individuals with broad ecological distributions. In spite of the nonpolyploidization of the hybrid, its formation is a long-term evolutionary process rather than a product of a recent disturbance, and considering other sympatric zones in Epidendrum, these events could be recurrent. PMID:24198942

  8. The feeding zones of terrestrial planets and insights into Moon formation

    NASA Astrophysics Data System (ADS)

    Kaib, Nathan A.; Cowan, Nicolas B.

    2015-05-01

    The final stage of terrestrial planet formation consists of several hundred approximately lunar mass bodies accreting into a few terrestrial planets. This final stage is stochastic, making it hard to predict which parts of the original planetesimal disk contributed to each of our terrestrial planets. Here we present an extensive suite of terrestrial planet formation simulations that allows quantitative analysis of this process. Although there is a general correlation between a planet's location and the initial semi-major axes of its constituent planetesimals, we concur with previous studies that Venus, Earth, and Mars analogs have overlapping, stochastic feeding zones. We quantify the feeding zone width, Δa , as the mass-weighted standard deviation of the initial semi-major axes of the planetary embryos and planetesimals that make up the final planet. The size of a planet's feeding zone in our simulations does not correlate with its final mass or semi-major axis, suggesting there is no systematic trend between a planet's mass and its volatile inventory. Instead, we find that the feeding zone of any planet more massive than 0.1M⊕ is roughly proportional to the radial extent of the initial disk from which it formed: Δa ≈ 0.25 (amax -amin) , where amin and amax are the inner and outer edge of the initial planetesimal disk. These wide stochastic feeding zones have significant consequences for the origin of the Moon, since the canonical scenario predicts the Moon should be primarily composed of material from Earth's last major impactor (Theia), yet its isotopic composition is indistinguishable from Earth. In particular, we find that the feeding zones of Theia analogs are significantly more stochastic than the planetary analogs. Depending on our assumed initial distribution of oxygen isotopes within the planetesimal disk, we find a ∼ 5% or less probability that the Earth and Theia will form with an isotopic difference equal to or smaller than the Earth and Moon

  9. Oceanic crust formation in the Egeria Fracture Zone Complex (Central Indian Ocean)

    NASA Astrophysics Data System (ADS)

    Le Minor, Marine; Gaina, Carmen; Sigloch, Karin; Minakov, Alexander

    2016-04-01

    This study aims to analyse in detail the oceanic crust fabric and volcanic features (seamounts) formed for the last 10 million years at the Central Indian Ridge between 19 and 21 latitude south. Multibeam bathymetry and magnetic data has been collected in 2013 as part of the French-German expedition RHUM-RUM (Reunion hotspot and upper mantle - Reunion's unterer mantel). Three long profiles perpendicular on the Central Indian Ridge (CIR), south of the Egeria fracture zone, document the formation of oceanic crust since 10 million years, along with changes in plate kinematics and variations in the magmatic input. We have inspected the abyssal hill geometry and orientation along conjugate oceanic flanks and within one fracture zone segment where we could identify J-shaped features that are indicators of changes in plate kinematics. The magnetic anomaly data shows a slight asymmetry in seafloor spreading rates on conjugate flanks: while a steady increase in spreading rate from 10 Ma to the present is shown by the western flank, the eastern part displays a slowing down from 5 Ma onwards. The deflection of the anti J-shaped abyssal hill lineations suggest that the left-stepping Egeria fracture zone complex (including the Egeria, Flinders and an un-named fracture zone to the southeast) was under transpression from 9 to 6 Ma and under transtension since 3 Ma. The transpressional event was triggered by a clockwise mid-ocean ridge reorientation and a decrease of its offset, whereas the transtensional regime was probably due to a counter-clockwise change in the spreading direction and an increase of the ridge offset. The new multibeam data along the three profiles reveal that crust on the eastern side is smoother (as shown by the abyssal hill number and structure) and hosts several seamounts (with age estimations of 7.67, 6.10 and 0.79 Ma), in contrast to the rougher conjugate western flank. Considering that the western flank was closer to the Reunion plume, and therefore

  10. Contact resistance and normal zone formation in coated yttrium barium copper oxide superconductors

    NASA Astrophysics Data System (ADS)

    Duckworth, Robert Calvin

    2001-11-01

    This project presents a systematic study of contact resistance and normal zone formation in silver coated YBa2CU3Ox (YBCO) superconductors. A unique opportunity exists in YBCO superconductors because of the ability to use oxygen annealing to influence the interfacial properties and the planar geometry of this type of superconductor to characterize the contact resistance between the silver and YBCO. The interface represents a region that current must cross when normal zones form in the superconductor and a high contact resistance could impede the current transfer or produce excess Joule heating that would result in premature quench or damage of the sample. While it has been shown in single-crystalline YBCO processing methods that the contact resistance of the silver/YBCO interface can be influenced by post-process oxygen annealing, this has not previously been confirmed for high-density films, nor for samples with complete layers of silver deposited on top of the YBCO. Both the influence of contact resistance and the knowledge of normal zone formation on conductor sized samples is essential for their successful implementation into superconducting applications such as transmission lines and magnets. While normal zone formation and propagation have been studied in other high temperature superconductors, the amount of information with respect to YBCO has been very limited. This study establishes that the processing method for the YBCO does not affect the contact resistance and mirrors the dependence of contact resistance on oxygen annealing temperature observed in earlier work. It has also been experimentally confirmed that the current transfer length provides an effective representation of the contact resistance when compared to more direct measurements using the traditional four-wire method. Finally for samples with low contact resistance, a combination of experiments and modeling demonstrate an accurate understanding of the key role of silver thickness and substrate

  11. Model for Transition Zone Formation from Upwelling Thermo-Chemical Plumes of Intermediate Rheology

    NASA Astrophysics Data System (ADS)

    Nguyen, C. T.; Weeraratne, D. S.

    2008-12-01

    The mantle transition zone has been limited to a layer of approximately 250 km at the base of the upper mantle, identified by studies in seismology and mineral physics. However, there are many uncertainties as to the nature of formation of this mid-mantle layer, its evolution over geological time, physical properties, and its role facilitating or inhibiting whole mantle flow. Here, we conduct laboratory fluid experiments using high viscosity corn syrup fluids and liquid gallium to study mantle convection processes in the early Earth. Specifically, we consider early core formation events involving metal-silicate plumes which sink following impact events and entrain magma ocean material from the surface during descent. Preliminary studies indicate that low viscosity, buoyant material, that makes up the model magma ocean near the surface is entrained in conduits that form behind quickly descending liquid metal plumes to the base of the lower mantle. This low density material brought to the base of the model lower mantle becomes buoyant and subsequently rises back up to the top of the fluid box forming a new intermediate material that has experienced both chemical and thermal diffusion along its mantle pathway and empties at the top of the lower mantle or base of a magma ocean. Two-component fluid experiments are considered in the presence of a hot lower thermal boundary layer at Rayleigh numbers of 103 to 105 and low Reynolds number flow, and indicate that upwelling thermo-chemical plumes may form following core formation events. This new third fluid layer of intermediate rheology is considered as a model for the mantle transition zone. Shadow graph images indicate a sharp density contrast with surrounding fluids that persists for long times, consistent with seismic discontinuities observed for the Earth's transition zone. We will present quantitative estimates of material rheology, density, and flow properties for scaling with a silicate mantle, geophysical, and

  12. Investigating the Role of Dehydration Reactions in Subduction Zone Pore Pressures Using Newly-Developed Permeability-Porosity Relationships

    NASA Astrophysics Data System (ADS)

    Screaton, E.; Daigle, H.; James, S.; Meridth, L.; Jaeger, J. M.; Villaseñor, T. G.

    2014-12-01

    Dehydration reactions are linked to shallow subduction zone deformation through excess pore pressures and their effect on mechanical properties. Two reactions, the transformation of smectite to illite and of opal-A to opal-CT and then to quartz, can occur relatively early in the subduction process and may affect the propagation of the plate boundary fault, the updip limit of velocity-weakening frictional paper, and tsunamigenesis. Due to large variations between subduction zones in heat flow, sedimentation rates, and geometries, dehydration location may peak prior to subduction to as much as 100 km landward of the deformation front. The location of the dehydration reaction peak relative to when compaction occurs, causes significant differences in pore pressure generation. As a result, a key element to modeling excess pore pressures due to dehydration reactions is the assumed relationship between permeability and porosity. Data from Integrated Ocean Drilling Program (IODP) drilling of subduction zone reference sites were combined with previously collected results to develop relationships for porosity-permeability behavior for various sediment types. Comparison with measurements of deeper analog data show that porosity-permeability trends are maintained through burial and diagenesis to porosities <10%, suggesting that behavior observed in shallow samples is informative for predicting behavior at depth following subduction. We integrate these permeability-porosity relationships, compaction behavior, predictions of temperature distribution, kinetic expressions for smectite and opal-A dehydration, into fluid flow models to examine the role of dehydration reactions in pore pressure generation.

  13. Clay surface catalysis of formation of humic substances: potential role of maillard reactions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mechanisms of the formation of humic substances are poorly understood, especially the condensation of amino acids and reducing sugars products (Maillard reaction) in soil environments. Clay minerals behave as Lewis and Brönsted acids and catalyze several reactions and likely to catalyze the Mai...

  14. Evidence of reaction rate influencing cubic and hexagonal phase formation process in CdS nanocrystals

    NASA Astrophysics Data System (ADS)

    Deka, Kuldeep; Kalita, M. P. C.

    2016-05-01

    CdS nanocrystals are synthesized by co-precipitation method using 2-mercaptoethanol (ME) as capping agent. Cubic, hexagonal and their mixture are obtained by varying the ME concentration. Lower (higher) ME concentration results in cubic (hexagonal) phase. The crystallite sizes are in the range 3-7 nm. Increase in ME concentration lead to lower reaction rate between Cd2+ and S2- of the precursors, and slower reaction rate is found to favor hexagonal phase formation over the cubic one in CdS nanocrystals. Role of reaction rate in the phase formation process provides a way to synthesize CdS nanocrystals in desired crystal phase.

  15. Redox reactions and complex formation of transplutonium elements in solutions

    SciTech Connect

    Krot, N.N.; Myasoedov, B.F.

    1986-01-01

    This paper gives a brief analysis of the kinetics and mechanism of a number of redox processes and the complex formation of transplutonium elements in unusual oxidation states. The composition and strength of complexes of TPE with various addends have been determined. The new experimental data on the oxidation potentials of americium and berkelium ions in solutions are cited in abbreviated form. It follows from the data that in phosphoric acid solutions, when the H/sub 3/PO/sub 4/ concentration is increased from 10 to 15 M, the oxidation potential of the couple Am(IV)-Am(III) decreases. The oxidation potentials of the couples Am(VI)-Am(V), Cm(V)-Cm(IV), and Bk(IV)Bk(III) are also presented.

  16. Conditions of kyanite formation from fluid in an alpine shear zone

    NASA Astrophysics Data System (ADS)

    Schultze, Dina; Loges, Anselm; Franz, Gerhard

    2014-05-01

    Hydrothermally formed quartz-kyanite rocks from the WSW-ENE-striking Greiner shear zone (Pfitscher Joch, Italy) on the south-western border of Tauern window were investigated in order to reconstruct conditions and processes of kyanite formation from metamorphic fluids. It is known from experiments that kyanite does not precipitate spontaneously from a qz-saturated, Al-rich fluid in spite of p-T conditions well inside the thermodynamic stability field of kyanite. Natural samples where kyanite nucleates spontaneously from fluid were investigated in order to understand what factors may control inhibition of nucleation in experiments. The Greiner shear zone cuts a variety of metasedimentary (metapelites, -psammites) units of the lower Schieferhülle, which lie between two distinct Zentralgneis units (Tuxer gneiss core in the north, Zillertaler gneiss core in the south). At the Pfitscher Joch near to the Rotbachlspitze (2897 m), the shear zone intersects the tectonic contact between the Schieferhülle metasediments and the Zillertaler gneiss in an acute angle. A number of segregations (up to 1m in diameter) composed mainly of quartz, feldspar and tourmaline are found along strike in the most silica-rich sheared stratigraphic layers. Besides kyanite and quartz the vein rocks show a range of other refractory mineral phases, especially pyrophyllite, rutile and zircon. Minor amounts of xenotime and monazite represent the REE carrier in these rocks. Growth textures indicate simultaneous crystallization of quartz, kyanite, rutile and zircon, whereas pyrophyllite may represent alteration processes in a later stage during obduction of the rocks. Additionally, in some samples muscovite and tourmaline were observed. The potassium and boron supply is likely provided by the metapelite or gneiss units adjacent to the shear zone. In the metapelites tourmaline is most abundant in the vicinity of the shear zone, suggesting migration of boron-rich fluids either to or from the shear zone

  17. The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

    USGS Publications Warehouse

    Jaisi, D.P.; Eberl, D.D.; Dong, H.; Kim, J.

    2011-01-01

    The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65??C) were the most favorable conditions forthe formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

  18. Evaluating the Influence of Chemical Reactions on Wellbore Cement Integrity and Geochemical Tracer Behavior in Hydraulically-Fractured Shale Formations

    NASA Astrophysics Data System (ADS)

    Verba, C.; Lieuallen, A.; Yang, J.; Torres, M. E.; Hakala, A.

    2014-12-01

    Ensuring wellbore integrity for hydraulically-fractured shale reservoirs is important for maintaining zonal isolation of gases and fluids within the reservoir. Chemical reactions between wellbore cements, the shale formation, formation fluids, and fracturing fluids could affect the ability for cement to form an adequate seal. This study focuses on experimental investigations to evaluate how cement, rock, brines, and fracturing fluids react under conditions similar to the perforated zone associated with the Marcellus shale (Greene County, Pennsylvania). Two pressure/temperature regimes were investigated- moderate (25 MPa, 50oC) and high (27.5 MPa, 90oC). Shale collected from the Lower Marcellus section was encased in Class A cement, cured for 24 hours, and then exposed to simulated conditions in experimental autoclave reactors. The simulated formation fluid was a synthetic brine, modeled after a flowback fluid contained 187,000 mg/l total dissolved solids and had a pH of 7.6. The effect of pH was probed to evaluate the potential for cement reactivity under different pH conditions, and the potential for contaminant or geochemical tracer release from the shale (e.g. arsenic and rare earth elements). In addition to dissolution reactions, sorption and precipitation reactions between solutes and the cement are being evaluated, as the cement could bond with solute-phase species during continued hydration. The cements are expected to show different reactivity under the two temperature conditions because the primary cement hydration product, calcium silicate hydrate (C-S-H) is heavily influenced by temperature. Results from these experimental studies will be used both to inform the potential changes in cement chemistry that may occur along a wellbore in the hydraulically-fractured portion of a reservoir, and the types of geochemical tracers that may be useful in tracking these reactions.

  19. Polycyclic aromatic hydrocarbon (PAH) formation from benzyl radicals: a reaction kinetics study.

    PubMed

    Sinha, Sourab; Raj, Abhijeet

    2016-03-01

    The role of resonantly stabilized radicals such as propargyl, cyclopentadienyl and benzyl in the formation of aromatic hydrocarbons such as benzene and naphthalene in the high temperature environments has been long known. In this work, the possibility of benzyl recombination to form three-ring aromatics, phenanthrene and anthracene, is explored. A reaction mechanism for it is developed, where reaction energetics are calculated using density functional theory (B3LYP functional with 6-311++G(d,p) basis set) and CBS-QB3, while temperature-dependent reaction kinetics are evaluated using transition state theory. The mechanism begins with barrierless formation of bibenzyl from two benzyl radicals with the release of 283.2 kJ mol(-1) of reaction energy. The further reactions involve H-abstraction by a H atom, H-desorption, H-migration, and ring closure to gain aromaticity. Through mechanism and rate of production analyses, the important reactions leading to phenanthrene and anthracene formation are determined. Phenanthrene is found to be the major product at high temperatures. Premixed laminar flame simulations are carried out by including the proposed reactions for phenanthrene formation from benzyl radicals and compared to experimentally observed species profiles to understand their effects on species concentrations. PMID:26923612

  20. Formation of polycyclic aromatic hydrocarbons from bimolecular reactions of phenyl radicals at high temperatures.

    PubMed

    Constantinidis, P; Schmitt, H-C; Fischer, I; Yan, B; Rijs, A M

    2015-11-21

    The self-reaction of the phenyl radical is one of the key reactions in combustion chemistry. Here we study this reaction in a high-temperature flow reactor by IR/UV ion dip spectroscopy, using free electron laser radiation as mid-infrared source. We identified several major reaction products based on their infrared spectra, among them indene, 1,2-dihydronaphthalene, naphthalene, biphenyl and para-terphenyl. Due to the structural sensitivity of the method, the reaction products were identified isomer-selectively. The work shows that the formation of indene and naphthalene, which was previously considered to be evidence for the HACA (hydrogen abstraction C2H2 addition) mechanism in the formation of polycyclic aromatic hydrocarbons and soot can also be understood in a phenyl addition model. PMID:26457393

  1. Paleomagnetism of Harutagawa formation in the Hohi Volcanic Zone in northeastern part of Kyushu Island, Japan

    NASA Astrophysics Data System (ADS)

    Kudou, T.; Shibuya, H.

    2008-12-01

    The Beppu-Shimabara graben in the Hohi Volcanic Zone (HVZ) in northeastern part of Kyushu Island, Japan is thought to be a volcano-tectonic depression. Volcanic stratigraphy and age studies of the area have unraveled the late Pliocene structural formation history of HVZ (e.g. Kamata, 1994, Kido, 2007). The age and sedimentation rate of lacustrine deposits in HVZ is one of the keys for interpreting the temporal relation between the formation of Beppu-Shimabara graben and the huge pyroclastic flows appeared in the area. We study the magnetostratigraphy of the Harutagawa formation, which is one of those lacustrine deposits. The formation is dominated by conglomerates and mad stones to siltstones, in the lower and upper parts, respectively, but bares many tuff layers all over the formation. Fission track ages of two tuff layers, one is from lower part and the other is from upper part of Harutagawa formation, are determined as 3.86 ± 0.77Ma and 3.6 ± 0.2Ma, respectively (Kido, 2007). Samples for paleomagnetic analyses have been collected at 28 sites in several continuous outcrop of the Harutagawa formation. The sites are set to be spaced equally in the stratigraphy. Samples were collected by a portable electric motor drill. A few pilot specimens from each site are subjected to progressive thermal and alternating field (AF) demagnetization. However, AF demagnetization is not effective. All remaining specimens are, therefore, submitted to the progressive thermal demagnetization. The samples have mean magnetic intensity of 1.7 × 10- 4A/m and 7.7 × 10-5A/m before and after demagnetization, respectively. Samples from 6 sites have no stable component or are thought to be completely remagnetized by the present magnetic field. As the result, 22 sites are determined their polarities; 8 were reversed and 14 were normal. The normal polarity sites were correlative to Sidufjall, Nunivak and Cochiti subchrons in the Gilbert reversed polarity chron. This correlation indicates that

  2. Simulations of Pore Formation in Lipid Membranes: Reaction Coordinates, Convergence, Hysteresis, and Finite-Size Effects.

    PubMed

    Awasthi, Neha; Hub, Jochen S

    2016-07-12

    Transmembrane pores play an important role in various biophysical processes such as membrane permeation, membrane fusion, and antimicrobial peptide activity. In principal, all-atom molecular dynamics (MD) simulations provide an accurate model of pore formation in lipid membranes. However, the free energy landscape of transmembrane pore formation remains poorly understood, partly because potential of mean force (PMF) calculations of pore formation strongly depend on the choice of the reaction coordinate. In this study, we used umbrella sampling to compute PMFs for pore formation using three different reaction coordinates, namely, (i) a coordinate that steers the lipids in the lateral direction away from the pore center, (ii) the distance of a single lipid phosphate group from the membrane center, and (iii) the average water density inside a membrane-spanning cylinder. Our results show that while the three reaction coordinates efficiently form pores in membranes, they suffer from strong hysteresis between pore-opening and pore-closing simulations, suggesting that they do not restrain the systems close to the transition state for pore formation. The two reaction coordinates that act via restraining the lipids lead to more pronounced hysteresis compared with the coordinate acting on the water molecules. By comparing PMFs computed from membranes with different numbers of lipids, we observed significant artifacts from the periodic boundary conditions in small simulation systems. Further analysis suggests that the formation and disruption of a continuous hydrogen-bonding network across the membrane corresponds to the transition state for pore formation. Our study provides molecular insights into the critical steps of transmembrane pore formation, and it may guide the development of efficient reaction coordinates for pore formation. PMID:27254744

  3. EXFOR basics: A short guide to the nuclear reaction data exchange format

    SciTech Connect

    McLane, V.

    1996-07-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data.

  4. Formation of Fragment Rich Pseudotachylite Zones During Central Uplift Formation in the Vredefort Impact Structure, South Africa

    NASA Astrophysics Data System (ADS)

    Lieger, D.; Riller, U.; Reimold, W. U.; Gibson, R. L.

    Field-based structural analysis of the Vredefort Dome focused on mapping of pre-impact planar mineral fabrics and structural properties of fragment-rich pseudotachylite zones, such as geometry, orientation, brecciation intensity of the zones.

  5. The sensitivity of mechanical properties of TFRS composites to variations in reaction zone size and properties. [Tungsten Fiber Reinforced Superalloys

    NASA Technical Reports Server (NTRS)

    Craddock, James N.; Hopkins, Dale A.; Petrasek, Donald W.; Brindley, Pamela K.

    1987-01-01

    The properties of tungsten fiber reinforced superalloys (TFRS) composites are calculated using a 3-component micromechanical model. The properties and size of the reaction zone are varied and the effect of these variations on the composite properties are studied. Results are presented in graphical and tabular form. Post-matrix yield behavior is examined in terms of the tangent modulus of the composite and measures of the effective strength of the lamina.

  6. Reaction layer formation at the graphite/copper-chromium alloy interface

    NASA Technical Reports Server (NTRS)

    Devincent, Sandra M.; Michal, Gary M.

    1993-01-01

    Sessile drop tests were used to obtain information about copper chromium alloys that suitably wet graphite. Characterization of graphite/copper-chromium alloy interfaces subjected to elevated temperatures were conducted using scanning electron micrography, energy dispersive spectroscopy, Auger electron spectroscopy, and X-ray diffraction analyses. These analyses indicate that during sessile drop tests conducted at 1130 C for one hour, copper alloys containing greater than 0.98 percent chromium form continuous reaction layers of approximately 10 micron thickness. The reaction layers adhere to the graphite surface. The copper wets the reaction layer to form a contact angle of 60 degrees or less. X-ray diffraction results indicate that the reaction layer is chromium carbide. The kinetics of reaction layer formation were modelled in terms of bulk diffusion mechanisms. Reaction layer thickness is controlled initially by the diffusion of Cr out of Cu alloy and later by the diffusion of C through chromium carbide.

  7. Reaction layer formation at the graphite/copper-chromium alloy interface

    NASA Technical Reports Server (NTRS)

    Devincent, Sandra M.; Michal, Gary M.

    1992-01-01

    Sessile drop tests were used to obtain information about copper chromium alloys that suitably wet graphite. Characterization of graphite/copper-chromium alloy interfaces subjected to elevated temperatures were conducted using scanning electron micrography, energy dispersive spectroscopy, auger electron spectroscopy, and x ray diffraction analyses. These analyses indicate that during sessile drop tests conducted at 1130 C for one hour, copper alloys containing greater than 0.98 percent chromium form continuous reaction layers of approximately 10 micron thickness. The reaction layers adhere to the graphite surface. The copper wets the reaction layer to form a contact angle of 60 degrees or less. X ray diffraction results indicate that the reaction layer is chromium carbide. The kinetics of reaction layer formation were modelled in terms of bulk diffusion mechanisms. Reaction layer thickness is controlled initially by the diffusion of Cr out of Cu alloy and later by the diffusion of C through chromium carbide.

  8. Formation of HCN+ in Heterogeneous Reactions of N2+ and N+ with Surface Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Harnisch, Martina; Keim, Alan; Scheier, Paul; Herman, Zdenek

    2013-10-01

    A significant increase of the ion yield at m/z 27 in collisions of low-energy ions of N2+ and N+ with hydrocarbon-covered room-temperature or heated surfaces of tungsten, carbon-fiber composite, and beryllium, not observed in analogous collisions of Ar+, is ascribed to the formation of HCN+ in heterogeneous reactions between N2+ or N+ and surface hydrocarbons. The formation of HCN+ in the reaction with N+ indicated an exothermic reaction with no activation barrier, likely to occur even at very low collision energies. In the reaction with N2+, the formation of HCN+ was observed to a different degree on these room-temperature and heated (150 and 300 °C) surfaces at incident energies above about 50 eV. This finding suggested an activation barrier or reaction endothermicity of the heterogeneous reaction of about 3-3.5 eV. The main process in N2+ or N+ interaction with the surfaces is ion neutralization; the probability of forming the reaction product HCN+ was very roughly estimated for both N2+ and N+ ions to about one in 104 collisions with the surfaces.

  9. Formation of harzburgite by pervasive melt/rock reaction in the upper mantle

    USGS Publications Warehouse

    Kelemen, P.B.; Dick, H.J.B.; Quick, J.E.

    1992-01-01

    Many mantle peridotite samples are too rich in SiO2 (in the form of orthopyroxene) and have ratios of light to heavy rare earth elements that are too high to be consistent with an origin as the residuum of partial melting of the primitive mantle. Trace element studies of melt/rock reaction zones in the Trinity peridotite provide evidence for reaction of the mantle lithosphere with ascending melts, which dissolved calcium-pyroxene and precipitated orthopyroxene as magma mass decreased. This process can account for the observed major and trace element compositions of lithospheric mantle samples, and may accordingly be prevalent in the upper mantle.

  10. Preprophase band formation and cortical division zone establishment: RanGAP behaves differently from microtubules during their band formation

    PubMed Central

    Yabuuchi, Takatoshi; Nakai, Tomonori; Sonobe, Seiji; Yamauchi, Daisuke; Mineyuki, Yoshinobu

    2015-01-01

    Correct positioning of the division plane is a prerequisite for plant morphogenesis. The preprophase band (PPB) is a key intracellular structure of division site determination. PPB forms in G2 phase as a broad band of microtubules (MTs) that narrows in prophase and specializes few-micrometer-wide cortical belt region, named the cortical division zone (CDZ), in late prophase. The PPB comprises several molecules, some of which act as MT band organization and others remain in the CDZ marking the correct insertion of the cell plate in telophase. Ran GTPase-activating protein (RanGAP) is accumulated in the CDZ and forms a RanGAP band in prophase. However, little is known about when and how RanGAPs gather in the CDZ, and especially with regard to their relationships to MT band formation. Here, we examined the spatial and temporal distribution of RanGAPs and MTs in the preprophase of onion root tip cells using confocal laser scanning microscopy and showed that the RanGAP band appeared in mid-prophase as the width of MT band was reduced to nearly 7 µm. Treatments with cytoskeletal inhibitors for 15 min caused thinning or broadening of the MT band but had little effects on RanGAP band in mid-prophase and most of late prophase cells. Detailed image analyses of the spatial distribution of RanGAP band and MT band showed that the RanGAP band positioned slightly beneath the MT band in mid-prophase. These results raise a possibility that RanGAP behaves differently from MTs during their band formation. PMID:26237087

  11. Formation of Zones with Maximum Supersonic Cavitation Intensity in Single-Component and Multicomponent Media

    NASA Astrophysics Data System (ADS)

    Bakhtin, B. I.; Ivashov, A. I.; Kuznetsov, A. V.; Skorokhodov, A. S.

    2016-05-01

    Experimental studies have been made on the formation of highly active cavitation zones in fluid media at high pressures (up to 6.5 MPa) and temperatures (up to 150°C) with the use of a high-power ultrasonic installation. It has been shown that attempts to increase the cavitation intensity in single-component and multicomponent media by increasing the power of the ultrasonic installation to above a certain limit lead to a strong degradation of the cavitation processes. This is due to the appearance of hydrodynamical flows generated by longitudinal vibrations of the installation radiator waveguide. Eliminating or weakening such flows makes it possible to increase markedly the efficiency of cavitation treatment by increasing the medium pressure (in the range of 0.5-1.5 MPa) and choosing the optimum ratio between the temperature of the medium and the power of the ultrasonic installation (specific acoustic power of the radiator). We recommend to use for the cavitation intensity index the acoustic activity of the cavitation zone (acoustic noise amplitude in the frequency range of 200 kHz-10 MHz), as well as its physical activity determined by the destruction rate of thin-layer indicators.

  12. Formation of Zones with Maximum Supersonic Cavitation Intensity in Single-Component and Multicomponent Media

    NASA Astrophysics Data System (ADS)

    Bakhtin, B. I.; Ivashov, A. I.; Kuznetsov, A. V.; Skorokhodov, A. S.

    2016-06-01

    Experimental studies have been made on the formation of highly active cavitation zones in fluid media at high pressures (up to 6.5 MPa) and temperatures (up to 150°C) with the use of a high-power ultrasonic installation. It has been shown that attempts to increase the cavitation intensity in single-component and multicomponent media by increasing the power of the ultrasonic installation to above a certain limit lead to a strong degradation of the cavitation processes. This is due to the appearance of hydrodynamical flows generated by longitudinal vibrations of the installation radiator waveguide. Eliminating or weakening such flows makes it possible to increase markedly the efficiency of cavitation treatment by increasing the medium pressure (in the range of 0.5-1.5 MPa) and choosing the optimum ratio between the temperature of the medium and the power of the ultrasonic installation (specific acoustic power of the radiator). We recommend to use for the cavitation intensity index the acoustic activity of the cavitation zone (acoustic noise amplitude in the frequency range of 200 kHz-10 MHz), as well as its physical activity determined by the destruction rate of thin-layer indicators.

  13. Reservoir characteristics of Putnam zone (Silurian Interlake Formation) lithofacies, southwestern Williston basin

    SciTech Connect

    Inden, R. ); Oglesby, C. ); Byrnes, A. ); Cluff, B. )

    1991-06-01

    Reservoirs in the Putnam zone (lower Interlake Formation) in the southwestern part of the Williston basin include oolitic-pellet dolomite grainstone, fossil-pellet grainstone, and a wide spectrum of reef-related, fossil-corral dolomite packstones and coral-stromatoporoid rudstone/boundstones. Each of these potential reservoirs has a unique pore system and, thus a different set of petrophysical properties which define their reservoir characteristics. Oolitic grainstones have a homogeneous intercrystalline-micro-crystalline pore system, whereas the fossil-pellet dolomite grainstone facies consists of separate mesovugs dispersed in well-interconnected intercrystalline porosity. Capillary pressure curves indicate that pore-throat heterogeneity is greater, and entry pressures lower, for reefal lithofacies than for pelletal grainstones. These curves also demonstrate why many of the producing fields tend to have high water cuts. In many oolitic-pellet grainstone units, irreducible water saturations of 10% would not be reached until a hydrocarbon column of 700 ft was reached. High water production characteristics are therefore expected because Red River/Interlake structures attain only 50-100 ft of closure. This, however, does not mean that Putnam is not an economic zone, especially as a secondary objective. Wells in Putnam and Crane fields, for instance, have reserves in excess of 300,000 bbl of oil. The reservoirs here may be dominated by the reef-related facies, which have an extremely high relative permeability to oil.

  14. Al-O complex formation in ion implanted Czochralski and floating-zone Si substrates

    NASA Astrophysics Data System (ADS)

    La Ferla, A.; Torrisi, L.; Galvagno, G.; Rimini, E.; Ciavola, G.; Carnera, A.; Gasparotto, A.

    1993-01-01

    Aluminum ions at 100 MeV were implanted into floating-zone (FZ) and Czochralski (CZ) grown Si substrates. At this energy the influence of the surface on the subsequent thermal treatment is negligible. In FZ samples the electrical active dose, as measured by spreading resistance profilometry, is independent of the annealing time at 1200 °C. In the CZ samples instead it considerably decreases with time. Secondary ion mass spectrometry analysis in CZ samples have revealed the presence of a multipeak structure around the projected range region for both Al and O signals. In FZ the structure is just detectable. The results imply that the Al-O complex formation is enhanced by the presence of oxygen but that it is catalyzed by the damage created during the implant. The carrier profiles coincide in both CZ and FZ diffused substrates by predeposition of Al from a solid source, i.e., in damage-free samples.

  15. Self-consistent formation of parallel electric fields in the auroral zone

    NASA Technical Reports Server (NTRS)

    Schriver, David; Ashour-Abdalla, Maha

    1993-01-01

    This paper presents results from a fully self-consistent kinetic particle simulation of the time-dependent formation of large scale parallel electric fields in the auroral zone. The results show that magnetic mirroring of the hot plasma that streams earthward from the magnetotail leads to a charge separation potential drop of many kilovolts, over an altitude range of a few thousand kilometers. Once the potential drop is formed, it remains relatively static and is maintained in time by the constant input of hot plasma from the tail; the parallel electric field accelerates ions away from Earth and ionospheric electrons towards the Earth. At altitudes above where the ions are mirror reflected and accelerated by the parallel electric field, low frequency waves are generated, possibly due to an ion/ion two-stream interaction.

  16. Deduction of compound nucleus formation probability from the fragment angular distributions in heavy-ion reactions

    NASA Astrophysics Data System (ADS)

    Yadav, C.; Thomas, R. G.; Mohanty, A. K.; Kapoor, S. S.

    2015-07-01

    The presence of various fissionlike reactions in heavy-ion induced reactions is a major hurdle in the path to laboratory synthesis of heavy and super-heavy nuclei. It is known that the cross section of forming a heavy evaporation residue in fusion reactions depends on the three factors—the capture cross section, probability of compound nucleus formation PCN, and the survival probability of the compound nucleus against fission. As the probability of compound nucleus formation, PCN is difficult to theoretically estimate because of its complex dependence on several parameters; attempts have been made in the past to deduce it from the fission fragment anisotropy data. In the present work, the fragment anisotropy data for a number of heavy-ion reactions are analyzed and it is found that deduction of PCN from the anisotropy data also requires the knowledge of the ratio of relaxation time of the K degree of freedom to pre-equilibrium fission time.

  17. Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area

    NASA Astrophysics Data System (ADS)

    Xu, Jun; Zhang, Yuanhang; Wang, Wei

    2006-12-01

    The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.

  18. [THE THROMBUS FORMATION IN THE PROSTHESIS AS A REACTION OF ORGANISM ON ITS MATERIAL].

    PubMed

    Alekseyeva, T A; Gupalo, Yu M; Kolomoets, A M; Lazarenko, O N; Lazarenko, G O; Litvin, P M; Lohs, I V; Smorzhevskiy, V J; Stepkin, V I

    2016-04-01

    Abstract Vascular prostheses, excised because of their functional properties loss, were studied. Using different methods there was established, that this complication is caused by the thrombus formation as a reaction of organism on the prosthesis material. The testing procedure on compatibility was proposed, using atomic-power microscope. Components of a patient immunity may identify the prosthesis material and start the rejection mechanisms in case of negative reaction. PMID:27434951

  19. Granular Shear Zone Formation: Acoustic Emission Measurements and Fiber-bundle Models

    NASA Astrophysics Data System (ADS)

    Michlmayr, Gernot; Or, Dani

    2013-04-01

    We couple the acoustic emissions method with conceptual models of granular material behavior for investigation of granular shear zone formation and to assess eminence of landslide hazard. When granular materials are mechanically loaded or sheared, they tend to produce discrete events of force network restructuring, and frictional interaction at grain contacts. Such abrupt perturbations within the granular lattice release part of the elastic energy stored in the strained material. Elastic waves generated by such events can be measured as acoustic emissions (AE) and may be used as surrogates for intermittent structural transitions associated with shear zone formation. To experimentally investigate the connection between granular shearing and acoustic signals we performed an array of strain-controlled shear-frame tests using glass beads. AE were measured with two different systems operating at two frequency ranges. High temporal resolution measurements of the shear stresses revealed the presence of small fluctuations typically associated with low-frequency (< 20 kHz) acoustic bursts. Shear stress jumps and linked acoustic signals give account of discrete events of grain network rearrangements and obey characteristic exponential frequency-size distributions. We found that statistical features of force jumps and AE events depend on mechanical boundary conditions and evolve during the straining process. Activity characteristics of high-frequency (> 30 kHz) AE events is linked to friction between grains. To interpret failure associated AE signals, we adapted a conceptual fiber-bundle model (FBM) that describes some of the salient statistical features of failure and associated energy production. Using FBMs for the abrupt mechanical response of the granular medium and an associated grain and force chain AE generation model provides us with a full description of the mechanical-acoustical granular shearing process. Highly resolved AE may serve as a diagnostic tool not only

  20. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms.

    PubMed

    Rasmussen, Helena; Sørensen, Hanne R; Meyer, Anne S

    2014-02-19

    The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes for the formation of HMF from glucose and three routes for furfural formation from xylose are possible. In addition, new findings show that biomass monosaccharides themselves can react further to form pseudo-lignin and humins as well as a wide array of other compounds when exposed to high temperatures. Hence, several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing strategies and forms an important basis for the development of new biorefinery products from lignocellulosic biomass as well. PMID:24412507

  1. Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

    NASA Astrophysics Data System (ADS)

    Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

    2010-11-01

    We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

  2. The Central Molecular Zone of the Milky Way: Lessons about Star Formation from an extreme Environment

    NASA Astrophysics Data System (ADS)

    Kauffmann, Jens; Thushara Pillai, G. S.; Zhang, Qizhou; Lu, Xing; Immer, Katharina

    2015-08-01

    The Central Molecular Zone of the Milky Way (CMZ; innermost ~100pc) hosts a number of remarkably dense and massive clouds. These are subject to extreme environmental conditions, including very high cosmic ray fluxes and strong magnetic fields. Exploring star formation under such exceptional circumstances is essential for several of reasons. First, the CMZ permits to probe an extreme point in the star formation parameter space, which helps to test theoretical models. Second, CMZ clouds might help to understand the star formation under extreme conditions in more distant environments, such as in starbursts and the early universe.One particularly striking aspect is that — compared to the solar neighborhood — CMZ star formation in dense gas is suppressed by more than an order of magnitude (Longmore et al. 2012, Kauffmann et al. 2013). This questions current explanations for relations between the dense gas and the star formation rate (e.g., Gao & Solomon 2004, Lada et al. 2012). In other words, the unusually dense and massive CMZ molecular clouds form only very few stars, if any at all. Why is this so?Based on data from ALMA, CARMA, and SMA interferometers, we present results from the Galactic Center Molecular Cloud Survey (GCMS), the first study of a comprehensive sample of molecular clouds in the CMZ. This research yields a curious result: most of the major CMZ clouds are essentially devoid of significant substructure of the sort usually found in regions of high-mass star formation (Kauffmann et al. 2013). Preliminary analysis indicates that some clouds rather resemble homogeneous balls of gas. This suggests a highly dynamic picture of cloud evolution in the CMZ where clouds form, disperse, and re-assemble constantly. This concept is benchmarked against a new ALMA survey and first results from a legacy survey on the SMA.It is plausible that dense clouds in other galaxies have a similar internal structure. Instruments like ALMA and the JWST will soon permit to

  3. Stream discharge events increase the reaction efficiency of the hyporheic zone of an in-stream gravel bar

    NASA Astrophysics Data System (ADS)

    Fleckenstein, J. H.; Trauth, N.; Schmidt, C.

    2015-12-01

    Streambed structures such as dunes, pool-riffles or bars enhance the exchange of stream water and solutes with the subsurface, the hyporheic zone. Prior studies have evaluated the factors which control hyporheic exchange and biogeochemical processes for steady state hydrological conditions using numerical models. However, the impact of natural discharge variability on water and solute exchange, creating hydraulically specific conditions for the reactions in the shallow streambed, has not been studied so far. In our study, we set up a transient flow and reactive transport model to elucidate the impact of single stream discharge events on water exchange, solute transport and reactions within the hyporheic zone of an in-stream gravel bar. The discharge events were varied by their duration and the maximum stream discharge. Temporally variable hydraulic heads were assigned as hydraulic head boundary conditions at the top of the reactive groundwater model MIN3P. A steady ambient groundwater flow field was introduced by lateral upstream and downstream hydraulic head boundaries, generating in combination with the stream water level, losing, neutral, or gaining stream conditions. Stream water borne dissolved oxygen, dissolved organic carbon and nitrate can infiltrate into the modelling domain across the top boundary and can react with each other by aerobic respiration and denitrification. Our results show that water and solute exchange through the hyporheic zone (only stream water that infiltrates into the subsurface and exfiltrates back to the stream) is highly dependent on the interplay between event characteristics and the ambient groundwater level. In scenarios where the stream discharge shifts the hydraulic system to strong and long-lasting losing conditions, hyporheic flow paths are longer and the extent of the hyporheic zone are deeper than under base flow conditions and small events where gaining conditions prevail. Consequently, stream discharge events may

  4. How can macromolecular crowding inhibit biological reactions? The enhanced formation of DNA nanoparticles

    PubMed Central

    Hou, Sen; Trochimczyk, Piotr; Sun, Lili; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Zhang, Xuzhu; Wielgus-Kutrowska, Beata; Bzowska, Agnieszka; Holyst, Robert

    2016-01-01

    In contrast to the already known effect that macromolecular crowding usually promotes biological reactions, solutions of PEG 6k at high concentrations stop the cleavage of DNA by HindIII enzyme, due to the formation of DNA nanoparticles. We characterized the DNA nanoparticles and probed the prerequisites for their formation using multiple techniques such as fluorescence correlation spectroscopy, dynamic light scattering, fluorescence analytical ultracentrifugation etc. In >25% PEG 6k solution, macromolecular crowding promotes the formation of DNA nanoparticles with dimensions of several hundreds of nanometers. The formation of DNA nanoparticles is a fast and reversible process. Both plasmid DNA (2686 bp) and double-stranded/single-stranded DNA fragment (66bp/nt) can form nanoparticles. We attribute the enhanced nanoparticle formation to the depletion effect of macromolecular crowding. This study presents our idea to enhance the formation of DNA nanoparticles by macromolecular crowding, providing the first step towards a final solution to efficient gene therapy. PMID:26903405

  5. How can macromolecular crowding inhibit biological reactions? The enhanced formation of DNA nanoparticles.

    PubMed

    Hou, Sen; Trochimczyk, Piotr; Sun, Lili; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Zhang, Xuzhu; Wielgus-Kutrowska, Beata; Bzowska, Agnieszka; Holyst, Robert

    2016-01-01

    In contrast to the already known effect that macromolecular crowding usually promotes biological reactions, solutions of PEG 6k at high concentrations stop the cleavage of DNA by HindIII enzyme, due to the formation of DNA nanoparticles. We characterized the DNA nanoparticles and probed the prerequisites for their formation using multiple techniques such as fluorescence correlation spectroscopy, dynamic light scattering, fluorescence analytical ultracentrifugation etc. In >25% PEG 6k solution, macromolecular crowding promotes the formation of DNA nanoparticles with dimensions of several hundreds of nanometers. The formation of DNA nanoparticles is a fast and reversible process. Both plasmid DNA (2686 bp) and double-stranded/single-stranded DNA fragment (66bp/nt) can form nanoparticles. We attribute the enhanced nanoparticle formation to the depletion effect of macromolecular crowding. This study presents our idea to enhance the formation of DNA nanoparticles by macromolecular crowding, providing the first step towards a final solution to efficient gene therapy. PMID:26903405

  6. Reaction Rates for the Formation of Deuterium Tritide from Deuterium and Tritium

    SciTech Connect

    McConville, G. T.; Menke, D. A.; Ellefson, R. E.

    1985-04-01

    The rates of formation of DT in a mixture of D2 and T2 have been measured as a function of initial T2 concentration, pressure, temperature,and methane concentration in a stainless steel reaction container which had been treated to inhibit protium ingrowth. An attempt has been made to explain the experimental resuts on the basis of ion-molecule chain reactions. Some of the observations are consistent with a gas-phase ion, ground-state molecule reaction, but some of the more interesting observations require more complicated models. The addition of excited state molecules or heterogeneous catalytic effects are possibilities that will need further experiments for confirmation.

  7. Denuded Zone Formation in Germanium Codoped Heavily Phosphorus-Doped Czochralski Silicon

    NASA Astrophysics Data System (ADS)

    Lin, Li-Xia; Chen, Jia-He; Wu, Peng; Zeng, Yu-Heng; Ma, Xiang-Yang; Yang, De-Ren

    2011-03-01

    The formation of a denuded zone (DZ) by conventional furnace annealing (CFA) and rapid thermal annealing (RTA) based denudation processing is investigated and the gettering of copper (Cu) atoms in germanium co-doped heavily phosphorus-doped Czochralski (GHPCZ) silicon wafers is evaluated. It is suggested that both a good quality defect-free DZ with a suitable width in the sub-surface area and a high density bulk micro-defect (BMD) region could be formed in heavily phosphorus-doped Czochralski (HPCZ) silicon and GHPCZ silicon wafers. This is ascribed to the formation of phosphorus-vacancy (P-V) related complexes and germanium-vacancy (GeV) related complexes. Compared with HPCZ silicon, the DZ width is wider in the GHPCZ silicon sample with CFA-based denudation processing but narrower in the one with two-step RTA pretreatments. These phenomena are ascribed to the enhancing effect of germanium on oxygen out-diffusion movement and oxygen precipitate nucleation, respectively. Furthermore, fairly clean DZs near the surface remain in both the HPCZ and GHPCZ silicon wafers after Cu in-diffusion, except for the HPCZ silicon wafer which underwent denudation processing with a CFA pretreatment, suggesting that germanium doping could improve the gettering of Cu contamination.

  8. Tetraspanin 7 regulates sealing zone formation and the bone-resorbing activity of osteoclasts.

    PubMed

    Kwon, Jun-Oh; Lee, Yong Deok; Kim, Haemin; Kim, Min Kyung; Song, Min-Kyoung; Lee, Zang Hee; Kim, Hong-Hee

    2016-09-01

    Tetraspanin family proteins regulate morphology, motility, fusion, and signaling in various cell types. We investigated the role of the tetraspanin 7 (Tspan7) isoform in the differentiation and function of osteoclasts. Tspan7 was up-regulated during osteoclastogenesis. When Tspan7 expression was reduced in primary precursor cells by siRNA-mediated gene knock-down, the generation of multinuclear osteoclasts was not affected. However, a striking cytoskeletal abnormality was observed: the formation of the podosome belt structure was inhibited and the microtubular network were disrupted by Tspan7 knock-down. Decreases in acetylated microtubules and levels of phosphorylated Src and Pyk2 in Tspan7 knock-down cells supported the involvement of Tspan7 in cytoskeletal rearrangement signaling in osteoclasts. This cytoskeletal defect interfered with sealing zone formation and subsequently the bone-resorbing activity of mature osteoclasts on dentin surfaces. Our results suggest that Tspan7 plays an important role in cytoskeletal organization required for the bone-resorbing function of osteoclasts by regulating signaling to Src, Pyk2, and microtubules. PMID:27416754

  9. Boundaries of intergrowths between mineral individuals: A zone of secondary mineral formation in aggregates

    NASA Astrophysics Data System (ADS)

    Brodskaya, R. L.; Bil'Skaya, I. V.; Lyakhnitskaya, V. D.; Markovsky, B. A.; Sidorov, E. G.

    2007-12-01

    Intergrowth boundaries between mineral individuals in dunite of the Gal’moenan massif in Koryakia was studied in terms of crystal morphology, crystal optics, and ontogenesis. The results obtained allowed us to trace the staged formation of olivine and chromite and four generations of these minerals. Micro-and nanotopography of boundary surfaces between intergrown mineral individuals of different generations was examined with optic, electron, and atomic force microscopes. The boundaries between mineral individuals of different generations are distinguished by their microsculpture for both olivine and chromite grains. Both minerals demonstrate a compositional trend toward refinement from older to younger generations. The decrease in the iron mole fraction in olivine and chromite is accompanied by the crystallization of magnetite along weakened zones in olivine of the first generation and as outer rims around the chromite grains of the second generation observable under optic and electronic microscopes. The subsequent refinement of chromite results in the release of PGE from its lattice, as established by atomic power microscopy. The newly formed PGM are localized at the boundaries between mineral individuals and, thus, mark a special stage in the ontogenetic evolution of mineral aggregates. Further recrystallization is expressed in the spatial redistribution of grain boundaries and the formation of monomineralic intergrowth boundaries, i.e., the glomerogranular structure of rock and substructures of PGM, chromite, and olivine grains as intermediate types of organization of the granular assemblies in the form of reticulate, chain, and cellular structures and substructures of aggregates.

  10. Substrate decomposition in galvanic displacement reaction: Contrast between gold and silver nanoparticle formation

    SciTech Connect

    Ghosh, Tapas; Satpati, Biswarup

    2015-06-24

    We have investigated substrate decomposition during formation of silver and gold nanoparticles in galvanic displacement reaction on germanium surfaces. Silver and gold nanoparticles were synthesized by electroless deposition on sputter coated germanium thin film (∼ 200 nm) grown initially on silicon substrate. The nanoparticles formation and the substrate corrosion were studied using scanning transmission electron microscopy (STEM) and the energy dispersive X-ray (EDX) spectroscopy.

  11. Substrate decomposition in galvanic displacement reaction: Contrast between gold and silver nanoparticle formation

    NASA Astrophysics Data System (ADS)

    Ghosh, Tapas; Kabiraj, D.; Satpati, Biswarup

    2015-06-01

    We have investigated substrate decomposition during formation of silver and gold nanoparticles in galvanic displacement reaction on germanium surfaces. Silver and gold nanoparticles were synthesized by electroless deposition on sputter coated germanium thin film (˜ 200 nm) grown initially on silicon substrate. The naoparticles formation and the substrate corrosion were studied using scanning transmission electron microscopy (STEM) and the energy dispersive X-ray (EDX) spectroscopy.

  12. Aqua-planet simulations of the formation of the South Atlantic convergence zone

    NASA Technical Reports Server (NTRS)

    Nieto Ferreira, Rosana; Chao, Winston C.

    2013-01-01

    The impact of Amazon Basin convection and cold fronts on the formation and maintenance of the South Atlantic convergence zone (SACZ) is studied using aqua-planet simulations with a general circulation model. In the model, a circular patch of warm sea-surface temperature (SST) is used to mimic the effect of the Amazon Basin on South American monsoon convection. The aqua-planet simulations were designed to study the effect of the strength and latitude of Amazon Basin convection on the formation of the SACZ. The simulations indicate that the strength of the SACZ increases as the Amazon convection intensifies and is moved away from the equator. Of the two controls studied here, the latitude of the Amazon convection exerts the strongest effect on the strength of the SACZ. An analysis of the synoptic-scale variability in the simulations shows the importance of frontal systems in the formation of the aqua-planet SACZ. Composite time series of frontal systems that occurred in the simulations show that a robust SACZ occurs when fronts penetrate into the subtropics and become stationary there as they cross eastward of the longitude of the Amazon Basin. Moisture convergence associated with these frontal systems produces rainfall not along the model SACZ region and along a large portion of the northern model Amazon Basin. Simulations in which the warm SST patch was too weak or too close to the equator did not produce frontal systems that extended into the tropics and became stationary, and did not form a SACZ. In the model, the SACZ forms as Amazon Basin convection strengthens and migrates far enough southward to allow frontal systems to penetrate into the tropics and stall over South America. This result is in agreement with observations that the SACZ tends to form after the onset of the monsoon season in the Amazon Basin.

  13. Thermal donor formation and annihilation in oxygen-implanted float-zone silicon

    SciTech Connect

    Hahn, S. ); Stein, H.J. ); Shatas, S.C. ); Ponce, F.A. )

    1992-09-01

    The formation and annihilation behaviors of thermal donors in {sup 16}O{sup +}-, {sup 18}O{sup +}-, or {sup 16}O{sup +}+{sup 12}C{sup +}-implanted float-zone silicon have been investigated with secondary ion mass spectrometry, spreading resistance probe, Hall effect, and transmission electron microscopy. Various oxygen or carbon+oxygen-implanted samples were laser annealed to remove implant damage and subjected to furnace annealing at 450 {degree}C for up to 100 h to activate oxygen-related thermal donors. Oxygen concentrations at the peak of the implanted profiles exceed the maximum for Czochralski Si by an order of magnitude. It is found that the third to fourth power dependence of thermal donor formation on oxygen generally observed for Czochralski Si does not hold for the higher oxygen concentration in the implanted layer. Annihilation characteristics of thermal donors formed in the oxygen implanted layers were investigated by the rapid thermal annealing technique. A rapid thermal anneal at 1150 {degree}C for 30 s was required to remove all the thermal donors. Based upon the annihilation kinetics data, it is tentatively concluded that both old and new thermal donors exist in the oxygen-implanted layer. For carbon+oxygen-coimplanted samples, the data have shown that carbon greatly increases the new thermal donor concentration in the implanted layer. Finally, precipitate morphologies for both oxygen-only- and carbon+oxygen-coimplanted samples after a 450 {degree}C furnace annealing were investigated by high resolution electron microscopy. In the case of oxygen-implant-only samples, predominant precipitate morphologies are needlelike while platelet defects predominate for carbon+oxygen-coimplanted samples. Since carbon increases the formation rate of new thermal donors, it is unlikely that they are distinctly related to needlelike precipitates as claimed in previous studies.

  14. Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation

    NASA Technical Reports Server (NTRS)

    Ferris, James P.; KAMALUDDIN

    1989-01-01

    The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

  15. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  16. IN VIVO FORMATION OF HALOGENATED REACTION PRODUCTS FOLLOWING PERORAL SODIUM HYPOCHLORITE

    EPA Science Inventory

    To date the principal concern of the disinfection of potable water has centered on the formation of halogenated organic reaction products and the adverse health effects that these products may have. However, an additional area for concern relating to water disinfection is the pot...

  17. THE OZONE REACTION WITH BUTADIENE: FORMATION OF TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    Abstract

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product ...

  18. Comparative Study Using Different Infrared Zones of the Solventless Activation of Organic Reactions

    PubMed Central

    Córdova, María Olivia Noguez; Flores Ramírez, Carlos I.; Bejarano, Benjamín Velasco; Arroyo Razo, Gabriel A.; Pérez Flores, Francisco J.; Tellez, Vladimir Carranza; Ruvalcaba, René Miranda

    2011-01-01

    In this work, the results of a study comparing the use of irradiation from different regions of the infrared spectrum for the promotion of several organic reactions, are presented and discussed. This use of eco-conditions provides a green approach to chemical synthesis. A set of ten different organic reactions were evaluated, including the Knoevenagel, Hantzsch, Biginelli and Meldrum reactions. It is important to highlight the use of a commercial device that produces infrared irradiation in the near infrared region and its distribution by convection providing heating uniformity, significantly reducing reaction times, achieving good yields and proceeding in the absence of solvent. It is also worth noting that a variety of different reactions may be performed at the same time. Finally, the products obtained were identified using TLC, together with corresponding MS-data, complementarily in comparison of NMR 1H and 13C data with literature information. PMID:22272092

  19. A quantitative approach to understanding amphibole reaction rims: Texture, mineralogy, and processes of formation

    NASA Astrophysics Data System (ADS)

    De Angelis, S. H.; Larsen, J. F.; Coombs, M. L.; Dunn, A.

    2012-12-01

    Amphibole is an important mineral present in many calc-alkaline volcanic deposits. A hydrous phase, volcanic amphibole is only stable at pressures greater than 100 MPa (approx. 4 km) and in melts containing at least 4 wt % H2O. When removed from their thermal and barometric stability field, amphiboles decompose to form aggregate rims of anhydrous minerals. Reaction rim thicknesses have been used to estimate timescales and rates of magma ascent, important parameters in determining eruptive style. However, the textures and mineralogy of reaction rims are complex; multiple forcing factors, such as heating and decompression, are responsible for their formation. Few studies have performed in-depth, systematic, and quantitative investigations of reaction rim textures and mineralogy: as a result, amphibole reaction rims are poorly understood. Based on natural reaction rims from Augustine Volcano Alaska, we have developed a new crystallization kinetics model for reaction rim formation in which the differences in reaction rim textures represent different degrees of forcing away from equilibrium. We present the results of an experimental study used to test this model. We performed experiments using a sintered high-silica andesite glass from the 2006 eruption of Augustine volcano. The starting powder was seeded with unrimmed amphibole phenocrysts. After at least 24 hours of equilibration at Augustine storage conditions (140 MPa/ 860oC), experiments were heated or decompressed. The experimental series experiments took samples to differing degrees of thermal of barometric instability, over different time scales, ranging from 3 hours to several days. The resulting reaction rims were analyzed using a variety of analytical imaging and X-ray mapping techniques. Reaction rims thickened and became more texturally and mineralogically complex as a result of 1) greater time spent outside of stability and; 2) the magnitude of instability experienced.

  20. A structured three-dimensional polymer electrolyte with enlarged active reaction zone for Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Bonnet-Mercier, Nadège; Wong, Raymond A.; Thomas, Morgan L.; Dutta, Arghya; Yamanaka, Keisuke; Yogi, Chihiro; Ohta, Toshiaki; Byon, Hye Ryung

    2014-11-01

    The application of conventional solid polymer electrolyte (SPE) to lithium-oxygen (Li-O2) batteries has suffered from a limited active reaction zone due to thick SPE and subsequent lack of O2 gas diffusion route in the positive electrode. Here we present a new design for a three-dimensional (3-D) SPE structure, incorporating a carbon nanotube (CNT) electrode, adapted for a gas-based energy storage system. The void spaces in the porous CNT/SPE film allow an increased depth of diffusion of O2 gas, providing an enlarged active reaction zone where Li+ ions, O2 gas, and electrons can interact. Furthermore, the thin SPE layer along the CNT, forming the core/shell nanostructure, aids in the smooth electron transfer when O2 gas approaches the CNT surface. Therefore, the 3-D CNT/SPE electrode structure enhances the capacity in the SPE-based Li-O2 cell. However, intrinsic instability of poly(ethylene oxide) (PEO) of the SPE matrix to superoxide (O2.-) and high voltage gives rise to severe side reactions, convincing us of the need for development of a more stable electrolyte for use in this CNT/SPE design.

  1. A structured three-dimensional polymer electrolyte with enlarged active reaction zone for Li–O2 batteries

    PubMed Central

    Bonnet-Mercier, Nadège; Wong, Raymond A.; Thomas, Morgan L.; Dutta, Arghya; Yamanaka, Keisuke; Yogi, Chihiro; Ohta, Toshiaki; Byon, Hye Ryung

    2014-01-01

    The application of conventional solid polymer electrolyte (SPE) to lithium-oxygen (Li–O2) batteries has suffered from a limited active reaction zone due to thick SPE and subsequent lack of O2 gas diffusion route in the positive electrode. Here we present a new design for a three-dimensional (3-D) SPE structure, incorporating a carbon nanotube (CNT) electrode, adapted for a gas-based energy storage system. The void spaces in the porous CNT/SPE film allow an increased depth of diffusion of O2 gas, providing an enlarged active reaction zone where Li+ ions, O2 gas, and electrons can interact. Furthermore, the thin SPE layer along the CNT, forming the core/shell nanostructure, aids in the smooth electron transfer when O2 gas approaches the CNT surface. Therefore, the 3-D CNT/SPE electrode structure enhances the capacity in the SPE-based Li–O2 cell. However, intrinsic instability of poly(ethylene oxide) (PEO) of the SPE matrix to superoxide (O2·−) and high voltage gives rise to severe side reactions, convincing us of the need for development of a more stable electrolyte for use in this CNT/SPE design. PMID:25410536

  2. Stratigraphic sections showing coal correlations within the lower coal zone of the Paleocene Fort Union Formation, Fillmore Ranch and Seaverson Reservoir quadrangles, Carbon County, Wyoming

    SciTech Connect

    Honey, J.G.; Hettinger, R.D.

    1989-01-01

    Stratigraphic sections showing coal correlations within the lower coal zone of the Paleocene Fort Union Formation, Fillmore Ranch and Seaverson Reservoir quadrangles, Carbon County, Wyoming are presented.

  3. Secondary organic aerosol formation initiated from reactions between ozone and surface-sorbed squalene

    NASA Astrophysics Data System (ADS)

    Wang, Chunyi; Waring, Michael S.

    2014-02-01

    Previous research has shown that ozone reactions on surface-sorbed D-limonene can promote gas phase secondary organic aerosol (SOA) formation indoors. In this work, we conducted 13 steady state chamber experiments to measure the SOA formation entirely initiated by ozone reactions with squalene sorbed to glass, at chamber ozone of 57-500 ppb for two relative humidity (RH) conditions of 21% and 51%, in the absence of seed particles. Squalene is a nonvolatile compound that is a component of human skin oil and prevalent on indoor surfaces and in settled dust due to desquamation. The size distributions, mass and number secondary emission rates (SER), aerosol mass fractions (AMF), and aerosol number fractions (ANF) of formed SOA were quantified. The surface AMF and ANF are defined as the change in SOA mass or number formed, respectively, per ozone mass consumed by ozone-squalene reactions. All experiments but one exhibited nucleation and mass formation. Mass formation was relatively small in magnitude and increased with ozone, most notably for the RH = 51% experiments. The surface AMF was a function of the chamber aerosol concentration, and a multi-product model was fit using the 'volatility basis set' framework. Number formation was relatively strong at low ozone and low RH conditions. Though we cannot extrapolate our results because experiments were conducted at high air exchange rates, we speculate that this process may enhance particle number more than mass concentrations indoors.

  4. Hierarchical data format (HDF5) for Modflow, Modpath and ZoneBudget

    NASA Astrophysics Data System (ADS)

    Cosemans, A.; Batelaan, O.; Louwyck, A.; Lermytte, J.

    2012-04-01

    More and more spatially detailed time dependent groundwater models are used and hence input files for models like Modflow (USGS) are becoming larger and larger. These input files are in ASCII format and contain datasets with values for each cell, changing often for each stress period. To diminish the problem of huge ASCII files, the datasets of the input files can be stored in an HDF5 file (Hierarchical data format). HDF5 is a data model, library and file format designed by HDFgroup for storing and managing data, flexible and efficient input and output and high volume and complex data. The file has a binary format and can be compressed with different kinds of compression methods. An HDF5 file consists among others of groups and datasets, referencing a dataset in the HDF5 file is similar to referencing a file in a folder of a file system. The contents of an HDF5 file can be viewed with HDFview, a Java-based viewer. HDF5 files can be constructed manually with the help of HDFview, or with the help of programming languages like C, C++, Matlab, Fortran or Python. The goal of this contribution is to show how HDF can improve data management of Modflow. A similar HDF5 link to Modflow has been implemented in the interface Groundwater Modeling System. Modflow has been extended to be able to read datasets from the ASCII input files which contain a reference to an HDF5 file for every real 1 or 2-dimensional dataset, every 2-dimensional integer dataset and the stress lists described in the Modflow user manual as U1DREL, U2DREL, U2DINT and ULSTRD. Two other programs from USGS, Modpath and Zonebudget, are also using partly the same input files as Modflow, and have been extended to be able to read the requested datasets from the HDF5 file. The total Modflow input file size, i.e. converted ASCII files and HDF5 file, will be decimated compared to the original size. Partly this is due to 'zlib' compression, 'zlib' is a free lossless data compression library. Due to faster reading of

  5. Combining direct residence time measurements and biogeochemistry to calculate in-situ reaction rates in the hyporheic zone

    NASA Astrophysics Data System (ADS)

    Pittroff, Marco; Gilfedder, Benjamin

    2015-04-01

    The hyporheic zone is an active interface between groundwater, riparian and surface water systems. Exchange and reaction of water, nutrients, and organic matter occur due to variations in surface and groundwater flow regimes, bed topography and active biogeochemistry fuelled by bioavailable carbon. There has been an increasing focus on coupling the residence time of surface water in the hyporheic zone with biogeochemical reactions. However, there are very few tracers that can be used to measure residence times in-situ, especially in complex groundwater-surface water settings. In this work we have used the natural radioisotope Radon (222Rn) as an in-situ tracer for river water residence time in a riffle-pool sequence (Rote Main River), and combined this information with biogeochemical parameters (DOC and C quality, O3, NO3, CO2). We can clearly observe a dependence of reaction progress on the water residence times, with oxygen and nitrate reduction following inverse logarithmic trends as a function of time. By comparing with initial concentrations (the river end member) with riverbed levels we have estimated first-order in-situ reduction rates for nitrate and oxygen. Nitrate reduction rates are at the higher end of published values, which is likely due to the continual supply of bioavailable carbon from the river system. This work helps to better understand the function and efficiency of the hyporheic zone as a natural filter for redox sensitive species such as nitrate at the groundwater - steam interface. It also provides a useful method for estimating residence times in complex, higher order river systems.

  6. Formation of lithospheric detachments: quantifying the mechanical effect of hydration reactions

    NASA Astrophysics Data System (ADS)

    Huet, Benjamin; Le Pourhiet, Laetitia; Yamato, Philippe; Watremez, Louise

    2015-04-01

    Many authors have published experimentally determined flow laws of rheologically important monophase aggregates and polyphase rocks. These laws provide good first order constraints on lithology-controlled lithospheric strength variations. However, since the whole range of mineralogical and chemical rock compositions cannot be experimentally tested, variations in reaction-controlled rock strength cannot be systematically and fully characterized. We here present the results of a study coupling thermodynamical and Thermomechanical modelling aiming at predicting the mechanical impact of metamorphic reactions on the strength of the mantle during its exhumation in rifted zones. Thermodynamic modelling is used for calculating the mineralogical composition of a typical peridotite as a function of pressure, temperature and water content. For a given P-T condition, the calculated modes and flow laws parameters for each phase constituting the paragenesis are then used as input of the Minimized Power Geometric model for predicting the polyphase aggregate strength. Hence, by considering P-T evolutions characteristic of exhumed mantle, we quantify the strength of the mantle as a function of pressure, temperature and hydration history in a rift zone. The mechanical impact of such metamorphic reactions and hydration is first quantified in 1D for three simplified hydration schemes and then introduced in preliminary 2D models which coupled fluid transfer to the thermodynamically derived rheological parameters. Schemes with limited hydratation are found to keep rocks in condition close to brittle ductile transition for a longer time and to permit more efficient mantle exhumation.

  7. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    SciTech Connect

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  8. A Kinetic Ladle Furnace Process Simulation Model: Effective Equilibrium Reaction Zone Model Using FactSage Macro Processing

    NASA Astrophysics Data System (ADS)

    Van Ende, Marie-Aline; Jung, In-Ho

    2016-05-01

    The ladle furnace (LF) is widely used in the secondary steelmaking process in particular for the de-sulfurization, alloying, and reheating of liquid steel prior to the casting process. The Effective Equilibrium Reaction Zone model using the FactSage macro processing code was applied to develop a kinetic LF process model. The slag/metal interactions, flux additions to slag, various metallic additions to steel, and arcing in the LF process were taken into account to describe the variations of chemistry and temperature of steel and slag. The LF operation data for several steel grades from different plants were accurately described using the present kinetic model.

  9. DOE capabilities for in-situ characterization and monitoring of formation properties in the vadose zone

    SciTech Connect

    Hearst, J.R.; Brodeur, J.R.; Koizumi, C.J.; Conaway, J.G.; Mikesell, J.L.; Nelson, P.H.; Stromswold, D.C.; Wilson, R.D.

    1993-09-01

    The DOE Environmental Restoration (ER) Program faces the difficult task of characterizing the properties of the subsurface and identifying and mapping a large number of contaminants at landfills, surface disposal areas, spill sites, nuclear waste tanks, and subsurface contaminant plumes throughout the complex of DOE facilities. Geophysical borehole logs can measure formation properties such as bulk density, water content, and lithology, and can quantitatively analyze for radionuclides and such elements as chlorine and heavy metals. Since these measurements can be replaced as desired, they can be used for both initial characterization and monitoring of changes in contaminant concentration and water content (sometimes linked to contaminant migration), at a fraction of the cost of conventional sampling. The techniques develop at several DOE laboratories, and the experience that the authors have gained in making in-situ measurements in the vadose zone, are applicable to problems at many other DOE sites. Moreover, they can capitalize on existing inventories of boreholes. By building on this experience workers involved in ER projects at those sites should be able to obtain high-quality data at substantial reductions in cost and time.

  10. On the feeding zone of planetesimal formation by the streaming instability

    SciTech Connect

    Yang, Chao-Chin; Johansen, Anders E-mail: anders@astro.lu.se

    2014-09-10

    The streaming instability is a promising mechanism to overcome the barriers in direct dust growth and lead to the formation of planetesimals. Most previous studies of the streaming instability, however, were focused on a local region of a protoplanetary disk with a limited simulation domain such that only one filamentary concentration of solids has been observed. The characteristic separation between filaments is therefore not known. To address this, we conduct the largest-scale simulations of the streaming instability to date, with computational domains up to 1.6 gas scale heights both horizontally and vertically. The large dynamical range allows the effect of vertical gas stratification to become prominent. We observe more frequent merging and splitting of filaments in simulation boxes of high vertical extent. We find multiple filamentary concentrations of solids with an average separation of about 0.2 local gas scale heights, much higher than the most unstable wavelength from linear stability analysis. This measures the characteristic separation of planetesimal forming events driven by the streaming instability and thus the initial feeding zone of planetesimals.

  11. Effect of grossular on garnet-biotite, Fe Mg exchange reactions: evidence from garnet with mixed growth and diffusion zoning

    NASA Astrophysics Data System (ADS)

    Alcock, J.

    1996-07-01

    Garnets that exhibit mixed growth and diffusion zoning are used to evaluate the effect of grossular content on garnet Fe Mg exchange reactions. These garnets from the uppermost amphibolite-facies to granulite-facies gneiss of the Wissahickon Group, southeastern Pennsylvania, show variation in grossular content (0.035< X Ca<0.14) but nearly constant Mg? ( X Mg/( X Mg+ X Fe) and X Mn through the interior indicating re-equilibration of garnet and matrix minerals with respect to iron, magnesium, and manganese. Mg? is not correlated with calcium content, evidence that the effect of calcium on garnet Fe Mg exchange reactions is small or is offset by other interactions in almandine-rich garnets. In either case, the data presented here indicate that correction for calcium content of garnets in the application of garnet-biotite geothermometry to high-grade metapelites is unnecessary and may lead to an overestimate of peak temperature.

  12. Spatial Heterogeneity and Imperfect Mixing in Chemical Reactions: Visualization of Density-Driven Pattern Formation

    DOE PAGESBeta

    Sobel, Sabrina G.; Hastings, Harold M.; Testa, Matthew

    2009-01-01

    Imore » mperfect mixing is a concern in industrial processes, everyday processes (mixing paint, bread machines), and in understanding salt water-fresh water mixing in ecosystems. The effects of imperfect mixing become evident in the unstirred ferroin-catalyzed Belousov-Zhabotinsky reaction, the prototype for chemical pattern formation. Over time, waves of oxidation (high ferriin concentration, blue) propagate into a background of low ferriin concentration (red); their structure reflects in part the history of mixing in the reaction vessel. However, it may be difficult to separate mixing effects from reaction effects. We describe a simpler model system for visualizing density-driven pattern formation in an essentially unmixed chemical system: the reaction of pale yellow Fe 3 + with colorless SCN − to form the blood-red Fe ( SCN ) 2 + complex ion in aqueous solution. Careful addition of one drop of Fe ( NO 3 ) 3 to KSCN yields striped patterns after several minutes. The patterns appear reminiscent of Rayleigh-Taylor instabilities and convection rolls, arguing that pattern formation is caused by density-driven mixing.« less

  13. Effect of gel network on pattern formation in the ferrocyanide-iodate-sulfite reaction.

    PubMed

    Ueno, Tomonaga; Yoshida, Ryo

    2011-06-01

    Stationary patterns have been researched experimentally since the discovery of the Turing pattern in the chlorite-iodide-malonic acid (CIMA) reaction and the self-replicating spot pattern in the ferrocyanide-iodate-sulfite (FIS) reaction. In this study, we reproduced the pattern formation in the FIS reaction by using poly(acrylamide) gels. Gels with different swelling ratios were prepared to use as a medium. The effect of the swelling ratio was compared with the effect of thickness. It was found that the swelling ratio greatly influenced pattern formation. Oscillating spot patterns appeared at high swelling ratios, and lamellar patterns appeared at a low swelling ratio. Self-replicating spot patterns appeared in between the two areas. The front velocities, which were observed in the initial stage of pattern formation, depended on the swelling ratio. Furthermore, this dependence obeys the free volume theory of diffusion. These results provide evidence that the change in front velocities is caused by a change in diffusion. Pattern formation can be controlled not only by thickness but also by swelling ratio, which may be useful for creating novel pattern templates. PMID:21557556

  14. Pattern formation on networks with reactions: A continuous-time random-walk approach

    NASA Astrophysics Data System (ADS)

    Angstmann, C. N.; Donnelly, I. C.; Henry, B. I.

    2013-03-01

    We derive the generalized master equation for reaction-diffusion on networks from an underlying stochastic process, the continuous time random walk (CTRW). The nontrivial incorporation of the reaction process into the CTRW is achieved by splitting the derivation into two stages. The reactions are treated as birth-death processes and the first stage of the derivation is at the single particle level, taking into account the death process, while the second stage considers an ensemble of these particles including the birth process. Using this model we have investigated different types of pattern formation across the vertices on a range of networks. Importantly, the CTRW defines the Laplacian operator on the network in a non-ad hoc manner and the pattern formation depends on the structure of this Laplacian. Here we focus attention on CTRWs with exponential waiting times for two cases: one in which the rate parameter is constant for all vertices and the other where the rate parameter is proportional to the vertex degree. This results in nonsymmetric and symmetric CTRW Laplacians, respectively. In the case of symmetric Laplacians, pattern formation follows from the Turing instability. However in nonsymmetric Laplacians, pattern formation may be possible with or without a Turing instability.

  15. Chemistry of polycyclic aromatic hydrocarbons formation from phenyl radical pyrolysis and reaction of phenyl and acetylene.

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

    An experimental investigation of phenyl radical pyrolysis and the phenyl radical + acetylene reaction has been performed to clarify the role of different reaction mechanisms involved in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) serving as precursors for soot formation. Experiments were conducted using GC/GC-MS diagnostics coupled to the high-pressure single-pulse shock tube present at the University of Illinois at Chicago. For the first time, comprehensive speciation of the major stable products, including small hydrocarbons and large PAH intermediates, was obtained over a wide range of pressures (25-60 atm) and temperatures (900-1800 K) which encompass the typical conditions in modern combustion devices. The experimental results were used to validate a comprehensive chemical kinetic model which provides relevant information on the chemistry associated with the formation of PAH compounds. In particular, the modeling results indicate that the o-benzyne chemistry is a key factor in the formation of multi-ring intermediates in phenyl radical pyrolysis. On the other hand, the PAHs from the phenyl + acetylene reaction are formed mainly through recombination between single-ring aromatics and through the hydrogen abstraction/acetylene addition mechanism. Polymerization is the common dominant process at high temperature conditions. PMID:22339468

  16. Secondary organic aerosol formation from ozone reactions with single terpenoids and terpenoid mixtures

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.; Wells, J. Raymond; Siegel, Jeffrey A.

    2011-08-01

    Ozone reacts with indoor-emitted terpenoids to form secondary organic aerosol (SOA). Most SOA research has focused on ozone reactions with single terpenoids or with consumer products, and this paper reports the results from an investigation of SOA formation from ozone reactions with both single terpenoids and mixtures of D-limonene, α-pinene, and α-terpineol. Transient experiments were conducted at low (25 ppb) and high (100 ppb) initial concentrations of ozone. The three terpenoids were tested singly and in combinations in a manner that controlled for their different reaction rates with ozone. The SOA formation was assessed by examining the evolution in time of the resulting number size-distributions and estimates of the mass concentrations. The results suggest that at higher ozone and terpenoid concentrations, SOA number formation follows a linear trend as a function of the initial rate of reaction. This finding was valid for both single terpenoids and mixtures. Generally speaking, higher ozone and terpenoid concentrations also led to larger geometric mean diameters and smaller geometric standard deviations of fitted lognormal distributions of the formed SOA. By assuming a density, mass concentrations were also assessed and did not follow as consistent of a trend. At low ozone concentration conditions, reactions with only D-limonene yielded the largest number concentrations of any experiment, even more than experiments with mixtures containing D-limonene and much higher overall terpenoid concentrations. This finding was not seen for high ozone concentrations. These experiments demonstrate quantifiable trends for SOA forming reactions of ozone and mixtures, and this work provides a framework for expanding these results to more complex mixtures and consumer products.

  17. Quantifying the ionic reaction channels in the Secondary Organic Aerosol formation from glyoxal

    NASA Astrophysics Data System (ADS)

    Maxut, Aurelia; Nozière, Barbara; Rossignol, Stéphanie; George, Christian; Waxman, Eleanor Marie; Laskin, Alexander; Slowik, Jay; Dommen, Josef; Prévôt, André; Baltensperger, Urs; Volkamer, Rainer

    2014-05-01

    Glyoxal, a common organic gas in the atmosphere, has been identified in recent years as an important Secondary Organic Aerosol (SOA) precursor (Volkamer et al., 2007). But, unlike with other precursors, the SOA is largely produced by particle-phase reactions (Volkamer et al., 2009) and equilibria (Kampf et al. 2013) that are still not entirely characterized. Since 2009 series of smog chamber experiments have been performed within the Eurochamp program at the Paul Scherrer Institute, Switzerland, to investigate SOA formation from glyoxal. In these experiments, glyoxal was produced by the gas-phase oxidation of acetylene in the presence of seeds, the seed composition and other conditions being varied. The 2011 campaign resulted in the identification of salting processes controlling the glyoxal partitioning in the seeds (Kampf et al. 2013). This presentation will report results of the 2013 campaign focusing on the identification of the various reactions (ionic or photo-induced) contributing to the SOA mass. In particular, the contribution of the ionic reactions, i.e. mediated by NH4+, were investigated by quantifying the formation of imidazoles (imidazole, imidazole-2-carboxaldehyde, 2,2'-biimidazole) from the small condensation channel of glyoxal with ammonia. For this, the SOA produced were collected on quartz filters and analyzed by Orbitrap LC/MS (Q-Exactive Thermo Fisher). The formation of other products such as organic acids was also investigated to determine potential competing reactions. Time-resolved MOUDI sampling coupled with nano-DESY/ESI-MS/MS analysis was also used to identify nitrogen- and sulphur-containing products from all the reactions. The results obtained for a range of conditions will be presented and compared with recent mechanistic information on the ionic reaction channels (Nozière et al., in preparation, 2013). The implementation of all this new information into a glyoxal-SOA model will be discussed.

  18. Photoinduced Vesicle Formation via the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction.

    PubMed

    Konetski, Danielle; Gong, Tao; Bowman, Christopher N

    2016-08-16

    Synthetic vesicles have a wide range of applications from drug and cosmetic delivery to artificial cell and membrane studies, making simple and controlled formation of vesicles a large focus of the field today. Here, we report the use of the photoinitiated copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction using visible light to introduce spatiotemporal control into the formation of vesicles. Upon the establishment of the spatiotemporal control over vesicle formation, it became possible to adjust initiation conditions to modulate vesicle sizes resulting in the formation of controllably small or large vesicles based on light intensity or giant vesicles when the formation was initiated in flow-free conditions. Additionally, this photoinitiated method enables vesicle formation at a density 400-fold higher than initiation using sodium ascorbate as the catalyst. Together, these advances enable the formation of high-density, controlled size vesicles using low-energy wavelengths while producing enhanced control over the formation characteristics of the vesicle. PMID:27443396

  19. Diffusion and reaction of pollutants in stratus clouds: application to nocturnal acid formation in plumes

    SciTech Connect

    Seigneur, C.; Saxena, P.; Mirabella, V.A.

    1985-09-01

    A mathematical model is presented that describes the transport, turbulent diffusion, and chemical reactions of air pollutants in stratus clouds. The chemical kinetic mechanism treats 97 gaseous, heterogeneous, and aqueous reactions between 54 species. The dispersion and night-time chemistry of a power plant plume in a stratus cloud is simulated. The contributions of various chemical pathways to the formation of sulfate and nitrate, the differences between plume and background concentrations, and the effect of reduced primary emissions on secondary pollutants are discussed. Calculated sulfate and nitrate concentrations are commensurate with measured atmospheric concentrations.

  20. Formation of Somitogenesis-like Pattern in a Reaction-Diffusion System

    NASA Astrophysics Data System (ADS)

    Sakamoto, Fumitaka; Miyakawa, Kenji

    2008-08-01

    The Belousov-Zhabotinsky reaction system showing stationary patterns is realized on the basis of water-in-oil microemulsions with the surfactant sodium bis(2-ethylhexyl)sulfosuccinate. We experimentally demonstrate the formation of somitogenesis-like pattern in which chemical waves arising from spontaneous bulk oscillations are successively arrested and then stacked. The experimental results are qualitatively reproduced by numerical simulations using the two-variable oregonator model. These show that a somitogenesis can be accounted for by the genuine reaction-diffusion model.

  1. Giant scour-fills in ancient channel-lobe transition zones: Formative processes and depositional architecture

    NASA Astrophysics Data System (ADS)

    Hofstra, M.; Hodgson, D. M.; Peakall, J.; Flint, S. S.

    2015-11-01

    Scours are common features of modern deep-marine seascapes, particularly downstream of the mouths of slope channels within channel-lobe transition zones (CLTZs). Their dimensions can exceed hundreds of metres in width and length, and tens of metres in depth. However, the stratigraphic architecture of large (> 100 m width) scours have not been described in detail from exhumed CLTZs. Here, the infill of two erosional features (0.5-1 km long and 15-20 m thick) from the Permian Karoo Basin succession, South Africa, are presented from palaeogeographically well-constrained CLTZs; one from Fan 3 in the Tanqua depocentre and one from Unit A5 in the Laingsburg depocentre. The basal erosion surfaces of the features are asymmetric with steep, undulating, and composite upstream margins, and low gradient simple downstream margins. The basal infill consists of thin-bedded siltstone and sandstone beds cut by closely-spaced scours; these beds are interpreted as partially reworked fine grained tails of bypassing flows with evidence for flow deflection. The erosional features are interpreted as giant scour-fills. The Unit A5 scour-fill shows a simple cut-and-fill history with lateral and upward transitions from siltstone- to sandstone-prone deposits. In contrast, the Fan 3 scour-fill shows headward erosion and lengthening of the scour surface suggesting temporal changes in the interaction between turbidity currents and the scour surface. This relationship could support the occurrence of a hydraulic jump during scour formation, whilst the majority of the fill represents deposition from subcritical flows. Different scour preservation mechanisms can be used to explain the style of infill. The architecture, sedimentary facies and palaeoflow patterns of the scour-fills are distinctly different from well documented adjacent basin-floor channel-fills at the same stratigraphic levels. The recognition of scour-fills helps to constrain their sedimentological and stratigraphic expression in

  2. First stage of CoSi{sub 2} formation during a solid-state reaction

    SciTech Connect

    Delattre, R.; Thomas, O.; Perrin-Pellegrino, C.; Rivero, C.; Simola, R.

    2014-12-28

    The kinetics of CoSi{sub 2} formation via a solid-state reaction between CoSi and single crystal Si has been the object of many studies in the past. Because of the importance of nucleation, complex kinetics has been reported. In this work, we investigate CoSi{sub 2} formation kinetics with in-situ diffraction during isothermal annealing of CoSi films on Si (100). In-situ measurements allow capturing the initial stage of CoSi{sub 2} formation. An initial t{sup 3/2} time-dependent evolution is observed and attributed to 3D growth of individual nuclei. This first regime is followed after the coalescence of the nuclei by a classical parabolic t{sup 1/2} one-dimensional film growth. We evidence a marked influence of the initial Co thickness (50 nm vs 10 nm) on the growth kinetics. A significant slowdown of the CoSi{sub 2} formation kinetics is observed for the thinnest film, whereas the activation energy remains the same. These results shine a new light on the complex formation kinetics of CoSi{sub 2} during solid-state reaction between CoSi and single crystal silicon and bring new knowledge about what occurs in the ultra-thin film regime, which is important for nanotechnologies.

  3. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    SciTech Connect

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  4. Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

    PubMed

    Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

    2014-01-21

    Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon. PMID:24351110

  5. Some new reaction pathways for the formation of cytosine in interstellar space - A quantum chemical study

    NASA Astrophysics Data System (ADS)

    Gupta, V. P.; Tandon, Poonam; Mishra, Priti

    2013-03-01

    The detection of nucleic acid bases in carbonaceous meteorites suggests that their formation and survival is possible outside of the Earth. Small N-heterocycles, including pyrimidine, purines and nucleobases, have been extensively sought in the interstellar medium. It has been suggested theoretically that reactions between some interstellar molecules may lead to the formation of cytosine, uracil and thymine though these processes involve significantly high potential barriers. We attempted therefore to use quantum chemical techniques to explore if cytosine can possibly form in the interstellar space by radical-radical and radical-molecule interaction schemes, both in the gas phase and in the grains, through barrier-less or low barrier pathways. Results of DFT calculations for the formation of cytosine starting from some of the simple molecules and radicals detected in the interstellar space are being reported. Global and local descriptors such as molecular hardness, softness and electrophilicity, and condensed Fukui functions and local philicity indices were used to understand the mechanistic aspects of chemical reaction. The presence and nature of weak bonds in the molecules and transition states formed during the reaction process have been ascertained using Bader's quantum theory of atoms in molecules (QTAIMs). Two exothermic reaction pathways starting from propynylidyne (CCCH) and cyanoacetylene (HCCCN), respectively, have been identified. While the first reaction path is found to be totally exothermic, it involves a barrier of 12.5 kcal/mol in the gas phase against the lowest value of about 32 kcal/mol reported in the literature. The second path is both exothermic and barrier-less. The later has, therefore, a greater probability of occurrence in the cold interstellar clouds (10-50 K).

  6. Reaction of furan-based o-quinodimethanes with triplet oxygen. Formation of cyclic peroxides

    SciTech Connect

    Chou, Chin-Hsing; Trahanovsky, W.S.

    1995-08-25

    Formation of cyclic peroxides 2a,2b, and 2c from the reactions of 2,3-dimethylene-2,3-dihydrofuran (1a) and the 5-methyl (1b) and 5-tert-butyl (1c) derivatives with triplet oxygen is reported. Thermolysis of cyclic peroxide 2c gives dialdehyde 5, hydroxy aldehydes 6 and 7, and diol 8 as products. 1 fig.

  7. Formation of O3/+/ by the reaction of metastable O2/+/ ions with O2

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; Pang, K. D.; Monahan, K. M.

    1974-01-01

    The high resolution of the photoionization mass spectrophotometer was utilized to resolve some doubts about the participating species in the reaction of metastable oxygen molecular ions with oxygen molecules to yield ozone ions and oxygen radicals. It is found from inspection of the appearance potential of the ozone ion that an a4 Pi-excited state is responsible for the formation of ozone near the appearance potential of these lines.

  8. Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose

    SciTech Connect

    Assary, Rajeev S.; Curtiss, Larry A.

    2011-10-19

    Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

  9. Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose

    SciTech Connect

    Assary, Rajeev S.; Curtiss, Larry A.

    2012-02-06

    Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

  10. Thermochemistry and reaction barriers for the formation of levoglucosenone from cellobiose.

    SciTech Connect

    Assary, R. S.; Curtiss, L. A.

    2012-02-06

    Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

  11. Applied velocity versus offset (VVO) to validated & characterized fracturing zone in intra Baturaja Formation, South Sumatera Basin

    NASA Astrophysics Data System (ADS)

    Mardiyan, Hilman; Rusli, Saifatur

    2016-01-01

    The velocity versus offset (VVO) as new geophysical method can be applied to detect some geological phenomenon, such as hydrocarbon trap, structural-fracture anomaly, facies changes, etc. The VVO method is data driven, based on the normal move out equation (NMO) and measuring the local event correlation between adjacent traces to get velocity gradient attributes which is derived from cross-plotting the velocity versus offset (VVO). This paper is describing applied VVO model that controlled by well data which indicated fracture from logs data, especially Resistivity Imager Logs or Formation Micro Imager (FMI). Images FMI logs data at Intra-Baturaja Carbonate Formation (BRF) in South Palembang Sub-basin (SPB), South Sumatera, shows vugs with fractures which orientation is roughly NNW-SSE. Meanwhile, the 2D NMO seismic gathers indicated those all as hockey stick at far offset. By applying VVO method, hockey stick can be identified and then used to validated, characterized and localized where the fracturing zone in intra-Baturaja Formation is. Laterally, VVO quantified as velocity gradient attribute which associated with geological model as the fracturing zone in study area. Characterization fracturing zone in Intra Baturaja Formation as geological lateral model by design is a challenging task for most exploration and production. In term of exploration where limited data is available, it can be used step ahead as carbonate fracture reservoir candidate in proven area and adjacent, especially in SPB South Sumatra.

  12. Proton Mobility in b₂ Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides.

    PubMed

    Nelson, Carissa R; Abutokaikah, Maha T; Harrison, Alex G; Bythell, Benjamin J

    2016-03-01

    A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting. PMID:26602904

  13. Proton Mobility in b2 Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides

    NASA Astrophysics Data System (ADS)

    Nelson, Carissa R.; Abutokaikah, Maha T.; Harrison, Alex G.; Bythell, Benjamin J.

    2016-03-01

    A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting.

  14. [Riboflavin-radical formation by mechanochemical solid-state reaction using stainless steel vessel].

    PubMed

    Kondo, Shin-ichi; Furuta, Youji; Okita, Shintarou; Sasai, Yasushi; Aramaki, Hideki; Kuzuya, Masayuki

    2004-03-01

    The mechanochemical reaction of free riboflavin (FR) due to vibratory ball milling was carried out in a stainless steel vessel at room temperature under anaerobic conditions. The ESR of the fractured sample showed a broad single-line spectrum. It is suggested that the solid-state single-electron transfer (SSET) reaction from the surface of the stainless steel vessel to FR proceeded during the vibratory milling, resulting in the formation of the corresponding anion radicals. When the mechanochemical reaction of FR in the presence of calcium pantothenate (PC) was carried out, the radical concentration increased with the increasing PC content. It was shown that the anion radical in the metal complex was stable for a lengthy period of time even in highly humid air. PMID:15049132

  15. Reaction pathways towards the formation of dolomite-analogues at ambient conditions

    NASA Astrophysics Data System (ADS)

    Pimentel, Carlos; Pina, Carlos M.

    2016-04-01

    In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

  16. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  17. Pattern formation in the iodate-sulfite-thiosulfate reaction-diffusion system.

    PubMed

    Liu, Haimiao; Pojman, John A; Zhao, Yuemin; Pan, Changwei; Zheng, Juhua; Yuan, Ling; Horváth, Attila K; Gao, Qingyu

    2012-01-01

    Sodium polyacrylate-induced pH pattern formation and starch-induced iodine pattern formation were investigated in the iodate-sulfite-thiosulfate (IST) reaction in a one-side fed disc gel reactor (OSFR). As binding agents of the autocatalyst of hydrogen ions or iodide ions, different content of sodium polyacrylate or starch has induced various types of pattern formation. We observed pH pulses, striped patterns, mixed spots and stripes, and hexagonal spots upon increasing the content of sodium polyacrylate and observed iodine pulses, branched patterns, and labyrinthine patterns upon increasing the starch content in the system. Coexistence of a pH front and an iodine front was also studied in a batch IST reaction-diffusion system. Both pH and iodine front instabilities were observed in the presence of sodium polyacrylate, i.e., cellular fronts and transient Turing structures resulting from the decrease in diffusion coefficients of activators. The mechanism of multiple feedback may explain the different patterns in the IST reaction-diffusion system. PMID:22068976

  18. Evidence of [eta]' or ordered zone formation in aluminum alloy 7075 from differential scanning calorimetry. [Aluminium alloy 7075

    SciTech Connect

    Bartges, C.W. )

    1993-05-01

    The development of high strength levels in Al-Mg-Zn-(Cu) alloys is dependent on the decomposition of the supersaturated solid solution ([alpha][sub ss]). The equilibrium phase, [eta], and the transition phase, [eta][prime], have compositions Mg(Zn, Al, Cu)[sub 2] and the GP Zones are solute rich clusters. Several authors have presented evidence that there is another precipitate which forms between the GP Zones and [eta][prime], though there is some controversy whether it is crystallographically distinct from the matrix, [eta][prime], or an ordered GP Zone. Regardless of their structure, these particles are seldom observed and are not usually considered in the decomposition of these alloys. Most of the previous observations of these particles have been the result of involved transmission electron microscopic and X-ray scattering experiments. This report shows they may also be detected using differential scanning calorimetry (DSC). Also significant is the fact that the particles were observed in AA 7075, an important commercial alloy. Lloyd and Chaturvedi also saw indications of [eta][prime] or ordered zones using DSC, but the results reported herein are different in several important respects. DSC traces of alloys aged for various times at room temperature and 121 C have shown there is at least one phase which can form during the decomposition of aluminum alloy 7075 that is not usually stated in the decomposition reaction. The results of previous studies suggest they may be ordered GP Zones or [eta][prime].

  19. Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals.

    PubMed

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600-1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. PMID:26270566

  20. Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

    PubMed Central

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. PMID:26270566

  1. Intimations of neck formation in heavy-ion subbarrier fusion reactions

    SciTech Connect

    Stelson, P.H.

    1990-07-01

    Since the observed fusion cross sections for collisions between heavy ions at subbarrier energies are orders of magnitude larger than would be expected for barrier tunnelling, one is faced with the task of identifying the basic force which is strong enough to overcome the strong Coulomb force and bring about fusion. The two possibilities seem to be excursions of the nuclear surface (and strong nuclear force) due to collective motions of the colliding nuclei and formation of a neck of nuclear matter. The first possibility has received the most attention. However, the systematics of fusion cross sections suggest neck formation is playing an important role. Neck formation can also result in a reseparation of the composite system and we review the experimental information on these reactions at barrier and subbarrier energies. 15 refs., 18 figs.

  2. Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

    PubMed

    Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

    2013-02-01

    The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent

  3. Modelling reaction front formation and oscillatory behaviour in a contaminant plume

    NASA Astrophysics Data System (ADS)

    Cribbin, Laura; Fowler, Andrew; Mitchell, Sarah; Winstanley, Henry

    2013-04-01

    Groundwater contamination is a concern in all industrialised countries that suffer countless spills and leaks of various contaminants. Often, the contaminated groundwater forms a plume that, under the influences of regional groundwater flow, could eventually migrate to streams or wells. This can have catastrophic consequences for human health and local wildlife. The process known as bioremediation removes pollutants in the contaminated groundwater through bacterial reactions. Microorganisms can transform the contaminant into less harmful metabolic products. It is important to be able to predict whether such bioremediation will be sufficient for the safe clean-up of a plume before it reaches wells or lakes. Borehole data from a contaminant plume which resulted from spillage at a coal carbonisation plant in Mansfield, England is the motivation behind modelling the properties of a contaminant plume. In the upper part of the plume, oxygen is consumed and a nitrate spike forms. Deep inside the plume, nitrate is depleted and oscillations of organic carbon and ammonium concentration profiles are observed. While there are various numerical models that predict the evolution of a contaminant plume, we aim to create a simplified model that captures the fundamental characteristics of the plume while being comparable in accuracy to the detailed numerical models that currently exist. To model the transport of a contaminant, we consider the redox reactions that occur in groundwater systems. These reactions deplete the contaminant while creating zones of dominant terminal electron accepting processes throughout the plume. The contaminant is depleted by a series of terminal electron acceptors, the order of which is typically oxygen, nitrate, manganese, iron, sulphate and carbon dioxide. We describe a reaction front, characteristic of a redox zone, by means of rapid reaction and slow diffusion. This aids in describing the depletion of oxygen in the upper part of the plume. To

  4. Imaging Proton Transfer and Dihalide Formation Pathways in Reactions of F– + CH3I

    PubMed Central

    2016-01-01

    Ion–molecule reactions of the type X– + CH3Y are commonly assumed to produce Y– through bimolecular nucleophilic substitution (SN2). Beyond this reaction, additional reaction products have been observed throughout the last decades and have been ascribed to different entrance channel geometries differing from the commonly assumed collinear approach. We have performed a crossed beam velocity map imaging experiment on the F– + CH3I reaction at different relative collision energies between 0.4 and 2.9 eV. We find three additional channels competing with nucleophilic substitution at high energies. Experimental branching ratios and angle- and energy differential cross sections are presented for each product channel. The proton transfer product CH2I– is the main reaction channel, which competes with nucleophilic substitution up to 2.9 eV relative collision energy. At this level, the second additional channel, the formation of IF– via halogen abstraction, becomes more efficient. In addition, we present the first evidence for an [FHI]− product ion. This [FHI]− product ion is present only for a narrow range of collision energies, indicating possible dissociation at high energies. All three products show a similar trend with respect to their velocity- and scattering angle distributions, with isotropic scattering and forward scattering of the product ions occurring at low and high energies, respectively. Reactions leading to all three reaction channels present a considerable amount of energy partitioning in product internal excitation. The internally excited fraction shows a collision energy dependence only for CH2I–. A similar trend is observed for the isoelectronic OH– + CH3I system. The comparison of our experimental data at 1.55 eV collision energy with a recent theoretical calculation for the same system shows a slightly higher fraction of internal excitation than predicted, which is, however, compatible within the experimental accuracy. PMID:26799548

  5. Imaging Proton Transfer and Dihalide Formation Pathways in Reactions of F(-) + CH3I.

    PubMed

    Carrascosa, Eduardo; Michaelsen, Tim; Stei, Martin; Bastian, Björn; Meyer, Jennifer; Mikosch, Jochen; Wester, Roland

    2016-07-14

    Ion-molecule reactions of the type X(-) + CH3Y are commonly assumed to produce Y(-) through bimolecular nucleophilic substitution (SN2). Beyond this reaction, additional reaction products have been observed throughout the last decades and have been ascribed to different entrance channel geometries differing from the commonly assumed collinear approach. We have performed a crossed beam velocity map imaging experiment on the F(-) + CH3I reaction at different relative collision energies between 0.4 and 2.9 eV. We find three additional channels competing with nucleophilic substitution at high energies. Experimental branching ratios and angle- and energy differential cross sections are presented for each product channel. The proton transfer product CH2I(-) is the main reaction channel, which competes with nucleophilic substitution up to 2.9 eV relative collision energy. At this level, the second additional channel, the formation of IF(-) via halogen abstraction, becomes more efficient. In addition, we present the first evidence for an [FHI](-) product ion. This [FHI](-) product ion is present only for a narrow range of collision energies, indicating possible dissociation at high energies. All three products show a similar trend with respect to their velocity- and scattering angle distributions, with isotropic scattering and forward scattering of the product ions occurring at low and high energies, respectively. Reactions leading to all three reaction channels present a considerable amount of energy partitioning in product internal excitation. The internally excited fraction shows a collision energy dependence only for CH2I(-). A similar trend is observed for the isoelectronic OH(-) + CH3I system. The comparison of our experimental data at 1.55 eV collision energy with a recent theoretical calculation for the same system shows a slightly higher fraction of internal excitation than predicted, which is, however, compatible within the experimental accuracy. PMID:26799548

  6. Formation processes of floe size distribution in the marginal ice zone (Invited)

    NASA Astrophysics Data System (ADS)

    Toyota, T.; Kohout, A.; Fraser, A.

    2013-12-01

    Since the marginal ice zone (MIZ) is the outer sea ice zone, its behavior is key to the understanding of the variability of sea ice extent associated with climate change. Especially for the melting processes in MIZ, where relatively small ice floes are dominant, floe size distribution (FSD) is an important parameter because smaller ice floes are subject to stronger lateral melting due to their larger cumulative perimeters. As the MIZ is characterized by vigorous interaction between sea ice and waves, breakup of sea ice due to flexural forcing and collisions is considered to play an essential role in the determination of FSD there. However, the available data have been very limited so far. Analysis of the observations of ice floes with a heli-borne video camera, focusing on the floe size ranging from 2 m to 100 m, in the Sea of Okhotsk, the Weddell Sea and off East Antarctica, revealed that while FSD is basically scale-invariant, a regime shift occurs at a size of about a few tens of meters, irrespective of the study region. It was also shown 1) that the floe size at which regime shift occurs slightly increases from 20 to 40 m with ice thickness, consistent with the theory of the flexural failure of sea ice; and 2) that to explain the scale invariance in FSD for smaller floes, a fragility of sea ice which is relevant to the strength of sea ice relative to waves can be a useful physical parameter to be correlated with the fractal dimension. Thus these results confirm the importance of wave-ice interaction to the formation of FSD. Based on this, a possible mechanism of the melting process was hypothesized that in the melting season sea ice extent retreats keeping the FSD relative to the ice edge nearly constant. As a next step and to confirm and further investigate this result, we planned to conduct the concurrent measurements of FSD, wave activities, and ice thickness off East Antarctica during the Sea Ice Physics and Ecosystem Experiment 2 (SIPEX2) in September to

  7. Early growth of Kohala volcano and formation of long Hawaiian rift zones

    USGS Publications Warehouse

    Lipman, P.W.; Calvert, A.T.

    2011-01-01

    Transitional-composition pillow basalts from the toe of the Hilo Ridge, collected from outcrop by submersible, have yielded the oldest ages known from the Island of Hawaii: 1138 ?? 34 to 1159 ?? 33 ka. Hilo Ridge has long been interpreted as a submarine rift zone of Mauna Kea, but the new ages validate proposals that it is the distal east rift zone of Kohala, the oldest subaerial volcano on the island. These ages constrain the inception of tholeiitic volcanism at Kohala, provide the first measured duration of tholeiitic shield building (???870 k.y.) for any Hawaiian volcano, and show that this 125-km-long rift zone developed to near-total length during early growth of Kohala. Long eastern-trending rift zones of Hawaiian volcanoes may follow fractures in oceanic crust activated by arching of the Hawaiian Swell in front of the propagating hotspot. ?? 2011 Geological Society of America.

  8. Revision of the 15N(p, γ)16O reaction rate and oxygen abundance in H-burning zones

    NASA Astrophysics Data System (ADS)

    Caciolli, A.; Mazzocchi, C.; Capogrosso, V.; Bemmerer, D.; Broggini, C.; Corvisiero, P.; Costantini, H.; Elekes, Z.; Formicola, A.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Imbriani, G.; Junker, M.; Lemut, A.; Marta, M.; Menegazzo, R.; Palmerini, S.; Prati, P.; Roca, V.; Rolfs, C.; Rossi Alvarez, C.; Somorjai, E.; Straniero, O.; Strieder, F.; Terrasi, F.; Trautvetter, H. P.; Vomiero, A.

    2011-09-01

    Context. The NO cycle takes place in the deepest layer of a H-burning core or shell, when the temperature exceeds T ≃ 30 × 106 K. The O depletion observed in some globular cluster giant stars, always associated with a Na enhancement, may be due to either a deep mixing during the red giant branch (RGB) phase of the star or to the pollution of the primordial gas by an early population of massive asymptotic giant branch (AGB) stars, whose chemical composition was modified by the hot bottom burning. In both cases, the NO cycle is responsible for the O depletion. Aims: The activation of this cycle depends on the rate of the 15N(p, γ)16O reaction. A precise evaluation of this reaction rate at temperatures as low as experienced in H-burning zones in stellar interiors is mandatory to understand the observed O abundances. Methods: We present a new measurement of the 15N(p, γ)16O reaction performed at LUNA covering for the first time the center of mass energy range 70-370 keV, which corresponds to stellar temperatures between 65 × 106 K and 780 × 106 K. This range includes the 15N(p, γ)16O Gamow-peak energy of explosive H-burning taking place in the external layer of a nova and the one of the hot bottom burning (HBB) nucleosynthesis occurring in massive AGB stars. Results: With the present data, we are also able to confirm the result of the previous R-matrix extrapolation. In particular, in the temperature range of astrophysical interest, the new rate is about a factor of 2 smaller than reported in the widely adopted compilation of reaction rates (NACRE or CF88) and the uncertainty is now reduced down to the 10% level.

  9. Sourcing Phenocrysts in Zoned Eruption Sequences Using Trace Elements: the Diego Hernandez Formation, Tenerife, Canary Islands

    NASA Astrophysics Data System (ADS)

    Wolff, J. A.; Neumann, E.

    2001-12-01

    The Diego Hernandez Formation (DHF) consists of several plinian fallout and ignimbrite sequences. With few exceptions, the dominant volume of each eruptive package consists of compositionally variable phonolite with smaller amounts of basaltic and intermediate components. In addition to mixing with the mafic components, compositional variations among the phonolitic component are due to crystal-liquid separation corresponding to up to 60% crystallization of a phonolitic starting liquid. Sphene crystallization plays a dominant role in controlling abundances of REE and HFSE among Tenerife phonolites. Sphene preferentially sequesters MREE, leading to strongly parabolic REE patterns among residual liquids. We have used this feature of the zoned Tenerife phonolites to match the REE content of individual pyroxene crystals, analyzed by laser ablation ICP-MS, to observed liquids using the elastic strain mineral-melt partitioning model of Blundy and Wood [1]. The strongly parabolic REE patterns of the liquids allow matching solely using the calculated Young's modulus of the host M2 cation site in pyroxene, without any independent constraint on the strain-free partition coefficient D0. For sodian salite pyroxenes in the phonolites, we find that most did not grow from the host liquid represented by the pumice clasts in which the crystals were erupted. Instead, most grew from liquids significantly more evolved, with lower MREE/LREE and MREE/HREE than the observed host. Elevated Zr contents in the salites support this conclusion, although the Zr abundances cannot be modelled with the same degree of confidence as the REE. The required liquids correspond to both the most-evolved phonolite compositions observed within the DHF, and to cognate syenite fragments found in the ignimbrites. Sodian salite also occurs as cores to titanaugite grains that grew from the basaltic component. These observations are consistent with a model in which invading basaltic magma melts syenite, and

  10. Reaction-path calculations of groundwater chemistry and mineral formation at Rainier Mesa, Nevada

    SciTech Connect

    Kerrisk, J F

    1983-12-01

    Reaction-patch calculations of groundwater chemistry and mineral formation at Rainier Mesa, Nevada, have been done using a model of volcanic-glass dissolution by water that is initially saturated with CO{sub 2}. In the reaction-path calculation, rate processes control the availability of species through dissolution of volcanic glass, and equilibrium processes distribute the species between the aqueous phase and mineral phases in equilibrium at each step in the reaction path. The EQ3/6 chemical-equilibrium programs were used for the calculation. Formation constants were estimated for three zeolites (clinoptilolite, mordenite, and heulandite), so they could be considered as possible mineral precipitates. The first stage of mineral evolution, from volcanic glass to a cristobalite, smectite clay, and zeolite mixture, was modeled quite well. Predicted aqueous-phase compositions and precipitates agree with observations at Rainier Mesa and other Nevada Test Site areas. Further mineral evolution, to quartz, clay, analcime, and albite mixtures, was also modeled. Decreasing aqueous silica activity from the first stage, where cristobalite precipitates, to later stages, where quartz is present, was the controlling variable in the mineral evolution. 30 references, 20 figures, 4 tables.

  11. Strain Partitioning into Dry and Wet Zones, and the Formation of Calcic Myrmekites in Syntectonic Syenites During High-T Crystallization/Deformation

    NASA Astrophysics Data System (ADS)

    De Toni, G. B.; Bitencourt, M. D. F.; Nardi, L. V. S.

    2014-12-01

    Myrmekites are fine intergrowths of (generally Na-rich) plagioclase and vermicular quartz developed on K-feldspar. The myrmekite-forming reaction is intimately related to deformation as it results in volume decrease and finer grainsize, thus enhancing plastic behaviour. In south Brazil, myrmekites are described in 642 Ma syntectonic syenites intrusive in a ca. 650 Ma collisional thrust pile comprised of granulite-facies gneisses. Syenites are porphyritic or fine-grained equigranular, with biotite, clinopyroxene (Cpx) and amphibole as mafic phases. They are variably deformed, and disposed in alternating m- to cm-thick layers. Within low-strain zones, well-developed magmatic foliation and lineation are marked by shape alignment of K-feldspar (Kf) and mafic minerals. Subgrains and recrystallized grains (ca. 0,5 mm) are common features at the border of Kf megacrysts, developed to different degrees. In highly deformed sites, the strain softening promoted by the inflow of late-magmatic fluids has lead to deformation partitioning into wet and dry zones, where different end-products are formed from a single syenite protolith. Within the dry zones, high-T recrystallization is abundant in both Kf and Cpx, but primary mineralogy is preserved. Within the wet zones the rock contains biotite and minor amphibole, but no Cpx. Kf megacrysts are progressively invaded by myrmekite (An38-43) mantles, especially along foliation-parallel faces. In their pressure shadows, 5mm-sized, subhedral plagioclase crystals (An44-48) containing irregular quartz inclusions are interpreted as crystallized from Ca-enriched, late-magmatic fluids which have destabilized Cpx. Large plagioclase crystals and myrmekite aggregates are further recrystallized, and the process has eventually lead to the formation of plagioclase-rich rocks restricted to m-thick bands. Deformation partitioning into dry and wet zones, and the fact that myrmekites are restricted to the latter demonstrate that fluids are the

  12. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia

    2008-08-01

    The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

  13. Secondary organic aerosol formation by self-reactions of methylglyoxal and glyoxal in evaporating droplets.

    PubMed

    De Haan, David O; Corrigan, Ashley L; Tolbert, Margaret A; Jimenez, Jose L; Wood, Stephanie E; Turley, Jacob J

    2009-11-01

    Glyoxal and methylglyoxal are scavenged by clouds, where a fraction of these compounds are oxidized during the lifetime of the droplet. As a cloud droplet evaporates, the remaining glyoxal and methylglyoxal must either form low-volatility compounds such as oligomers and remain in the aerosol phase, or transfer back to the gas phase. A series of experiments on evaporating aqueous aerosol droplets indicates that over the atmospherically relevant concentration range for clouds and fog (4-1000 microM), 33 +/- 11% of glyoxal and 19 +/- 13% of methylglyoxal remains in the aerosol phase while the remainder evaporates. Measurements of aerosol density and time-dependent AMS signal changes are consistent with the formation of oligomers by each compound during the drying process. Unlike glyoxal, which forms acetal oligomers, exact mass AMS data indicates that the majority of methylglyoxal oligomers are formed by aldol condensation reactions, likely catalyzed by pyruvic acid, formed from methylglyoxal disproportionation. Our measurements of evaporation fractions can be used to estimate the global aerosol formation potential of glyoxal and methylglyoxal via self-reactions at 1 and 1.6 Tg C yr(-1), respectively. This is a factor of 4 less than the SOA formed by these compounds if their uptake is assumed to be irreversible. However, these estimates are likely lower limits for their total aerosol formation potential because oxidants and amines will also react with glyoxal and methylglyoxal to form additional low-volatility products. PMID:19924942

  14. The formation and decay of superheavy nuclei produced in 48Ca-induced reactions

    NASA Astrophysics Data System (ADS)

    Kumar, Sushil; Balasubramaniam, M.; Gupta, Raj K.; Münzenberg, G.; Scheid, W.

    2003-04-01

    The formation of superheavy nuclei in 48Ca+232Th, 238U, 242,244Pu and 248Cm reactions and their subsequent decay are studied within the quantum mechanical fragmentation theory (QMFT) and the QMFT-based preformed cluster decay model (PCM) of Gupta and collaborators. According to QMFT, all these 48Ca-induced reactions are cold fusion reactions with relative excitation energies larger than those for the Pb-induced cold fusion reactions and smaller than those for the lighter beam, i.e. Mg, Si or S-induced hot fusion reactions. The same reactions were first suggested by Gupta et al in 1977 on the basis of QMFT, and this study re-establishes the same result. In fact, for such heavy isotopes of Z = 110 to 116, 50Ca is shown to be a better beam for cold fusion, but 50Ca is a radioactive nucleus. The alpha-decay half-lives of these nuclei after 3n and/or 4n evaporations, i.e. of the evaporation residues of these compound systems, calculated on PCM compare reasonably well with the experiments published by the Dubna group and another recent calculation. As expected for such rare decays, PCM calculations show that the alpha-preformation factors are small, ~10-8 to 10-10. The possible competition of alpha-decays with heavy cluster emissions from these superheavy nuclei is also probed from the point of view of searching for new nuclear structure information and possible future experiments with such exotic nuclei. The decay half-lives for some clusters are in fact shown to be lower than the limits of experiments for nuclei with enough available atoms.

  15. Fission and quasifission modes in heavy-ion-induced reactions leading to the formation of Hs{sup *}

    SciTech Connect

    Itkis, I. M.; Kozulin, E. M.; Itkis, M. G.; Knyazheva, G. N.; Bogachev, A. A.; Chernysheva, E. V.; Krupa, L.; Oganessian, Yu. Ts.; Zagrebaev, V. I.; Rusanov, A. Ya.; Goennenwein, F.; Dorvaux, O.; Stuttge, L.; Hanappe, F.; Vardaci, E.; Goes Brennand, E. de

    2011-06-15

    Mass and energy distributions of binary reaction products obtained in the reactions {sup 22}Ne+{sup 249}Cf,{sup 26}Mg+{sup 248}Cm, {sup 36}S+{sup 238}U, and {sup 58}Fe+{sup 208}Pb have been measured. All reactions lead to Hs isotopes. At energies below the Coulomb barrier the bimodal fission of Hs{sup *}, formed in the reaction {sup 26}Mg+{sup 248}Cm, is observed. In the reaction {sup 36}S+{sup 238}U, leading to the formation of a similar compound nucleus, the main part of the symmetric fragments arises from the quasifission process. At energies above the Coulomb barrier fusion-fission is the main process leading to the formation of symmetric fragments for both reactions with Mg and S ions. In the case of the {sup 58}Fe+{sup 208}Pb reaction the quasifission process dominates at all measured energies.

  16. Iterative reactions of transient boronic acids enable sequential C-C bond formation

    NASA Astrophysics Data System (ADS)

    Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.

    2016-04-01

    The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

  17. Dichotomous-noise-induced pattern formation in a reaction-diffusion system

    NASA Astrophysics Data System (ADS)

    Das, Debojyoti; Ray, Deb Shankar

    2013-06-01

    We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system.

  18. Phase formation during Mn thin film reaction with Ge: Self-aligned germanide process for spintronics

    NASA Astrophysics Data System (ADS)

    Abbes, O.; Portavoce, A.; Le Thanh, V.; Girardeaux, C.; Michez, L.

    2013-10-01

    Interesting results have been reported concerning the magnetic properties of the Mn5Ge3 compound, opening the road to possibly create spin injectors in Ge. However, a process compatible with the Complementary Metal Oxide Semiconductor technology, allowing to produce a Mn5Ge3 layer on the active regions of Ge-based transistors has not been well established yet. Here, we report on the solid state reaction between a 50 nm-thick Mn film and amorphous Ge, aiming to investigate a similar process than the one (Salicide) used for contact production in the standard Si technology. In situ X-ray diffraction combined with ex situ structural and magnetic characterizations were used to identify and study phase formation during the Mn/Ge reaction.

  19. Redirection of the Reaction Specificity of a Thermophilic Acetolactate Synthase toward Acetaldehyde Formation

    PubMed Central

    Cheng, Maria; Yoshiyasu, Hayato; Okano, Kenji; Ohtake, Hisao; Honda, Kohsuke

    2016-01-01

    Acetolactate synthase and pyruvate decarboxylase are thiamine pyrophosphate-dependent enzymes that convert pyruvate into acetolactate and acetaldehyde, respectively. Although the former are encoded in the genomes of many thermophiles and hyperthermophiles, the latter has been found only in mesophilic organisms. In this study, the reaction specificity of acetolactate synthase from Thermus thermophilus was redirected to catalyze acetaldehyde formation to develop a thermophilic pyruvate decarboxylase. Error-prone PCR and mutant library screening led to the identification of a quadruple mutant with 3.1-fold higher acetaldehyde-forming activity than the wild-type. Site-directed mutagenesis experiments revealed that the increased activity of the mutant was due to H474R amino acid substitution, which likely generated two new hydrogen bonds near the thiamine pyrophosphate-binding site. These hydrogen bonds might result in the better accessibility of H+ to the substrate-cofactor-enzyme intermediate and a shift in the reaction specificity of the enzyme. PMID:26731734

  20. Spatiotemporal Pattern Formation and Chaos in the Belousov-Zhabotinsky Reaction in a Reverse Microemulsion

    NASA Astrophysics Data System (ADS)

    Epstein, Irving R.; Vanag, Vladimir K.

    2003-08-01

    We study the spatiotemporal behavior of the oscillatory Belousov-Zhabotinsky (BZ) reaction in a reverse microemulsion consisting of water, octane and the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT). By varying the microemulsion composition, we can "tune" its structure, specifically the size and spacing between the nanometer-sized water droplets in which the polar BZ reactants reside. We find a remarkable array of pattern formation as the microemulsion structure and BZ chemistry are varied. Behaviors observed include stationary Turing patterns, traveling and standing waves, spirals, targets, antispirals and antitargets (which travel into rather than out from their center), and spatiotemporal chaos. A simple reaction-diffusion model, which accounts for the BZ chemistry and the differential diffusion of species within water droplets and in the bulk oil phase, is able to reproduce nearly all of the observed behavior.

  1. Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles

    DOE PAGESBeta

    Barron, S. C.; Knepper, R.; Walker, N.; Weihs, T. P.

    2011-01-11

    We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates (~1 K/s) using differential scanning calorimetry (DSC) traces to 725ºC. All three chemistries initially form a Ni-Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34-36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 105 K/s) inmore » high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (Tmax) are largely independent of foil chemistry at 0.6 ± 0.1 m/s and 1220 ± 50 K, respectively, and that the measured Tmax is more than 200 K lower than predicted adiabatic temperatures (Tad). The difference between Tmax and Tad is explained by the prediction that transformation to the final intermetallic phases occurs after Tmax and results in the release of 20-30 % of the total heat of reaction and a delay in rapid cooling.« less

  2. Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles

    SciTech Connect

    Barron, S. C.; Knepper, R.; Walker, N.; Weihs, T. P.

    2011-01-01

    We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates ({approx}1 K/s) using differential scanning calorimetry traces to 725 deg. C. All three chemistries initially form a Ni-Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34-36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 10{sup 5} K/s) in high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (T{sub max}) are largely independent of foil chemistry at 0.6{+-}0.1 m/s and 1220{+-}50 K, respectively, and that the measured T{sub max} is more than 200 K lower than predicted adiabatic temperatures (T{sub ad}). The difference between T{sub max} and T{sub ad} is explained by the prediction that transformation to the final intermetallic phases occurs after T{sub max} and results in the release of 20%-30% of the total heat of reaction and a delay in rapid cooling.

  3. TERRESTRIAL PLANET FORMATION AROUND THE CIRCUMBINARY HABITABLE ZONE: INWARD MIGRATION IN THE PLANETESIMAL SWARM

    SciTech Connect

    Gong Yanxiang; Zhou Jilin; Xie Jiwei E-mail: zhoujl@nju.edu.cn

    2013-01-20

    According to the core accretion theory, circumbinary embryos can form only beyond a critical semimajor axis (CSMA). However, due to the relatively high density of solid materials in the inner disk, a significant amount of small planetesimals must exist in the inner zone when embryos form outside this CSMA. Thus, embryo migration induced by the planetesimal swarm is possible after gas disk depletion. Through numerical simulations, we found that (1) the scattering-driven inward migration of embryos is robust and planets can form in the habitable zone if we adopt a mass distribution of an MMSN-like disk; (2) the total mass of the planetesimals in the inner region and continuous embryo-embryo scattering are two key factors that cause significant embryo migrations; and (3) the scattering-driven migration of embryos is a natural water-delivery mechanism. We propose that planet detections should focus on the close binary with its habitable zone near CSMA.

  4. Oligomer Formation Reactions of Criegee Intermediates in the Ozonolysis of Small Unsaturated Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Sakamoto, Y.; Inomata, S.; Hirokawa, J.

    2013-12-01

    Secondary organic aerosol (SOA) constitutes a substantial fraction of atmospheric fine particulate matters and has an effect on visibility, climate and human health. One of the major oxidizing processes leading to SOA formation is an ozonolysis of unsaturated hydrocarbons (UHCs).[1] Despite of its importance, the contribution of the ozonolysis of UHCs to the SOA formation in the troposphere is not sufficiently understood due to a lack of information on reaction pathways to produce low volatile compounds. While many studies have previously been focused on SOA formation from the ozonolysis of large UHCs, SOA formation from the ozonolysis of UHCs with less than six carbon atoms have been rarely investigated because their products are expected to be too volatile to contribute to the SOA formation. Very recently, a few studies have reported the SOA formation from the ozonolysis of such small UHCs but chemical mechanisms are still unclear. [2-4] In order to understand SOA formation from the ozonolysis of the small UHCs, this study investigated gas- and particle-phase products in laboratory experiments with a Teflon bag using a negative ion chemical ionization mass spectrometry (NI-CIMS) with chloride ion transfer for chemical ionization. This technique is suitable for analysis of compounds such as carboxylic acids and hydroperoxides expected to be produced in the ozonolysis of UHCs with less fragmentation, high selectivity, and high sensitivity. In the particle-phase analysis, SOAs collected on a PTFE filter were heated, and thermally desorbed compounds were analyzed. In the gas-phase analysis, series of peaks with an interval of a mass-to-charge ratio equal to the molecular weight of a Criegee intermediate formed in their ozonolysis were observed. These peaks were attributed to oligomeric hydroperoxides composed of Criegee intermediates as a chain unit. These oligomeric hydroperoxides were also observed in the particle-phase analysis, indicating that the oligomeric

  5. Search for reaction conditions and catalyst for selective prebiotic formation of Aldopentoses from Glycolaldehyde and Formaldehyde

    NASA Astrophysics Data System (ADS)

    Delidovich, Irina; Taran, Oxana; Parmon, Valentin; Gromov, Nikolay

    2012-07-01

    Formation of organic compounds from simple precursors appears to have been one of the first steps from geochemistry towards modern biochemistry. The Earth lagoons, hydrothermal springs, cosmic dust, meteorites, protoplanetary disk, etc. has been considered as the possible ``reactors'' in which the prebiotic synthesis could have taken place. The finding of reactions and reaction conditions which allow to produce the high yields of the biologically relevant substances from simple compounds could help us to verify different hypothesis of plausible prebotic conditions. In this work we have studied the formation of vitally important sugars, namely aldopentoses (ribose, xylose, lyxose and arabinose), from glycolaldehyde and formaldehyde over catalysts. Aldopentoses nowadays play the important roles as the components of polysaccharides, glycosides, nucleic acids and ATP. Glycolaldehyde is the simplest monosaccharide, which was found in the interstellar space [1], where it could be generated as a result of several processes, for instance, condensation of formaldehyde under UV-radiation [2]. In this work the peculiarities of interaction between glycolaldehyde and formaldehyde in the presence of soluble (phosphate and borate buffers) and solid (minerals apatite and montmorillonites) catalysts were studied. The dependences of composition of the reaction products on the catalyst nature, molar ratio of substrates, pH value of reaction mixture were revealed. The yields of aldopentoses amount to ca. 60-65% in the presence of borate catalyst under optimized reaction conditions. Borate acts not only as a catalyst, but also as the stabilizer of active intermediates and aldopentoses from side reactions [3]. Borates are present in some mineral and clays (serpentine, montmorillonite etc.) and in water of Cityhot springs (Geyser valley, placeKamchatka) in rather high concentrations. Therefore catalysis by borates could be considered as plausible prebotic condition. Acknowledgements. We

  6. Numerical simulation of formation of cyclone vortex flows in the intratropical zone of convergence and their early detection

    NASA Astrophysics Data System (ADS)

    Mingalev, I. V.; Astaf'eva, N. M.; Orlov, K. G.; Chechetkin, V. M.; Mingalev, V. S.; Mingalev, O. V.

    2012-05-01

    Mechanisms of formation of cyclonic vortices in the tropical atmosphere of the Earth are investigated in the intratropical zone of convergence using numerical simulation made with the complete system of equations of gas dynamics taking into account transport of infrared radiation, phase transitions of water vapor into microdrops of water and ice particles, and sedimentation of these drops and ice particles in the field of gravity force. Observational data on the structure of dominant air streams, which are formed in the intratropical zone of convergence over the North Atlantic in the periods of its highest thermodynamic intensity and instability, are used in the initial and boundary conditions of the model. Formation of cyclonic vortex flows is obtained numerically at sufficiently strong bending of the intratropical zone of convergence. The results of numerical modeling are compared with the data of satellite microwave monitoring: global radio thermal fields of the Earth from the electronic collection GLOBAL-Field allowing one to study the structure of atmospheric motions in a wide range of space-time scales.

  7. [Role of carotid chemoreceptors in formation of adaptive reactions in animals].

    PubMed

    Agadzhanian, N A; Elfimov, A I; Shevchenko, L V

    2003-01-01

    After surgical denervation of sinocarotid reflexogenic zones and bilateral glomectomy in white laboratory rats oxygen consumption, rectal temperature, rate of cardial contractions and thermoregulatory activity of skeletal muscles display authentic increase. Glomectomy results in decreasing calorigecic effect of noradrenaline. Compensatory increase of thermoregulatory activity of sceletal muscles in response to beta-adrenogenic blocade with inderal in post-glomectomic animals is authentically less, than before inactivation of carotid receptors. In animals after carotid glomectomy resistance to acute hypoxia is clearly reduced. True reduction of number of erythrocytes, of hemoglobin concentration, of hematocrite parameter in post glomectic animals was found, which indicates anemisation phenomena. It was found that glomectomy after adaptation of animals in the mountains of Tien Shan at the height of 3200 m during 30 days didn't substantively change resistance to acute hypoxia. Resistance to acute hypoxia of animals living on mountains (susliks, marmots) is higher than of animals living on plains. Glomectomy performed on animals living on mountain resulted in an insignificant decrease in resistance to acute hypoxia. Resistance to acute hypoxia in postglomectic animals was found to be directly linked with absolute amount of hemoglobin concentration and erythrocyte number. In that way denervation of sinocarotid reflexogenic zones and bilateral glomectomy is an adequate method of comparative research of functions regulation mechanism during formation of adaptive responses in animals in dependence of various factors of external environment in norm, as well, as in pathology. PMID:12918264

  8. Heterogeneous reactions of glyoxal on mineral particles: A new avenue for oligomers and organosulfate formation

    NASA Astrophysics Data System (ADS)

    Shen, Xiaoli; Wu, Huihui; Zhao, Yue; Huang, Dao; Huang, Liubin; Chen, Zhongming

    2016-04-01

    Glyoxal (GL) plays a crucial role in the formation of secondary organic aerosols (SOA), because it is highly water soluble and capable of oligomerization. This is the first study to describe irreversible heterogeneous reactions of GL on clean and acidic gas-aged SiO2, α-Al2O3, and CaCO3 particles, as models of real mineral particles, at various relative humidity and without irradiation and gas phase oxidants. A series of products, including oligomers, organosulfates, and organic acids, which contribute to SOA formation, were produced. GL uptake on SO2-aged α-Al2O3 enabled the oxidation of surface S(IV) to S(VI). The presence of adsorbed water on particles favored GL uptake and the formation of oligomers and organosulfate, but it suppressed organic acid formation. In addition, the aging process enhanced the positive effect of adsorbed water on GL uptake. These findings will further our understanding of the GL sink and SOA sources in the atmosphere.

  9. EXPERIMENTAL STUDY OF CO{sub 2} FORMATION BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES

    SciTech Connect

    Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira; Hama, Tetsuya; Pirronello, Valerio

    2010-04-01

    Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO{sub 2} was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO{sub 2} formation, due to reactions between CO and OH, occurs in tandem with H{sub 2}O formation, and this may lead to the formation of CO{sub 2} ice in polar environments, as typically observed in molecular clouds.

  10. FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

    EPA Science Inventory

    The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

  11. Nucleophilicity and P-C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex.

    PubMed

    Serrano, Ángel L; Casado, Miguel A; Ciriano, Miguel A; de Bruin, Bas; López, José A; Tejel, Cristina

    2016-01-19

    The diiridium complex [{Ir(ABPN2)(CO)}2(μ-CO)] (1; [ABPN2](-) = [(allyl)B(Pz)2(CH2PPh2)](-)) reacts with diphenylphosphane affording [Ir(ABPN2)(CO)(H) (PPh2)] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the terminal phosphanido lone pair to the HOMO of 2, indicating nucleophilic character of this ligand, which is evidenced by reactions of 2 with typical electrophiles such as H(+), Me(+), and O2. Products from the reaction of 2 with methyl chloroacetate were found to be either [Ir(ABPN2)(CO)(H)(PPh2CH2CO2Me)][PF6] ([6]PF6) or [Ir(ABPN2)(CO)(Cl)(H)] (7) and the free phosphane (PPh2CH2CO2Me), both involving P-C bond formation, depending on the reaction conditions. New complexes having iridacyclophosphapentenone and iridacyclophosphapentanone moieties result from reactions of 2 with dimethyl acetylenedicarboxylate and dimethyl maleate, respectively, as a consequence of a further incorporation of the carbonyl ligand. In this line, the terminal alkyne methyl propiolate gave a mixture of a similar iridacyclophosphapentanone complex and [Ir(ABPN2){CH═C(CO2Me)-CO}{PPh2-CH═CH(CO2Me)}] (10), which bears the functionalized phosphane PPh2-CH═CH(CO2Me) and an iridacyclobutenone fragment. Related model reactions aimed to confirm mechanistic proposals are also studied. PMID:26695592

  12. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes.

    PubMed

    Passananti, Monica; Kong, Lingdong; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; Chen, Jianmin; Donaldson, D James; George, Christian

    2016-08-22

    The heterogeneous reaction between SO2 and unsaturated compounds results in the efficient production of organosulfates for several fatty acids and long-chain alkenes. The presence of an acid group, the physical state of the reactants (solid or liquid), the nature of the double bond (cis, trans, terminal), and the use of light irradiation all have an impact on the reaction rate. The reaction was investigated using different set-ups (coated flow tube, aerosol flow tube, and diffuse reflectance infrared Fourier transform cell). The reaction products were identified by high-resolution mass spectrometry and the impact of this reaction on organosulfate formation in the atmosphere is discussed. PMID:27458109

  13. Formation of albitite-hosted uranium within IOCG systems: the Southern Breccia, Great Bear magmatic zone, Northwest Territories, Canada

    NASA Astrophysics Data System (ADS)

    Montreuil, Jean-François; Corriveau, Louise; Potter, Eric G.

    2015-03-01

    Uranium and polymetallic U mineralization hosted within brecciated albitites occurs one kilometer south of the magnetite-rich Au-Co-Bi-Cu NICO deposit in the southern Great Bear magmatic zone (GBMZ), Canada. Concentrations up to 1 wt% U are distributed throughout a 3 by 0.5 km albitization corridor defined as the Southern Breccia zone. Two distinct U mineralization events are observed. Primary uraninite precipitated with or without pyrite-chalcopyrite ± molybdenite within magnetite-ilmenite-biotite-K-feldspar-altered breccias during high-temperature potassic-iron alteration. Subsequently, pitchblende precipitated in earthy hematite-specular hematite-chlorite veins associated with a low-temperature iron-magnesium alteration. The uraninite-bearing mineralization postdates sodic (albite) and more localized high-temperature potassic-iron (biotite-magnetite ± K-feldspar) alteration yet predates potassic (K-feldspar), boron (tourmaline) and potassic-iron-magnesium (hematite ± K-feldspar ± chlorite) alteration. The Southern Breccia zone shares attributes of the Valhalla (Australia) and Lagoa Real (Brazil) albitite-hosted U deposits but contains greater iron oxide contents and lower contents of riebeckite and carbonates. Potassium, Ni, and Th are also enriched whereas Zr and Sr are depleted with respect to the aforementioned albitite-hosted U deposits. Field relationships, geochemical signatures and available U-Pb dates on pre-, syn- and post-mineralization intrusions place the development of the Southern Breccia and the NICO deposit as part of a single iron oxide alkali-altered (IOAA) system. In addition, this case example illustrates that albitite-hosted U deposits can form in albitization zones that predate base and precious metal ore zones in a single IOAA system and become traps for U and multiple metals once the tectonic regime favors fluid mixing and oxidation-reduction reactions.

  14. Peptide bond formation through gas-phase reactions in the interstellar medium: formamide and acetamide as prototypes

    SciTech Connect

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-09-20

    A theoretical study of the reactions of NH{sub 4}{sup +} with formaldehyde and CH{sub 5}{sup +} with formamide is carried out. The viability of these gas-phase ion-molecule reactions as possible sources of formamide and acetamide under the conditions of interstellar medium is evaluated. We report a theoretical estimation of the reaction enthalpies and an analysis of their potential energy surfaces. Formation of protonated formamide from the reaction between ammonium cation and formaldehyde is an exothermic process, but all the channels located on the potential energy surface leading to this product present net activation energies. For the reaction between methanium and formamide, different products are possible from a thermodynamic point of view. An analysis of its potential energy surface showed that formation of protonated acetamide and amino acetaldehyde takes place through barrier-free paths. Therefore, this reaction could be a feasible source of acetamide and amino acetaldehyde in space.

  15. Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan

    NASA Astrophysics Data System (ADS)

    Peng, Yajing; Ye, Yuqing; Liu, Jianyong; Lai, Weipeng

    2016-03-01

    A systematic investigations on the nitration of furoxan by two typical nitration reagents nitronium tetrafluoroborate (BF4NO2) and dilute nitric acid (HNO3) in chloroform (CHCl3) solvent using density functional theory (DFT) method to reveal the formation mechanism of 3,4-dinitrofuroxan (DNFO) and explore new synthesis routes. The geometry optimizations of the minima and transition states involved in the two nitration reactions are performed at the B3LYP/6-311++G** basis set level. The CCSD single-point energy corrections at the same level are carried out on top of the optimized geometries to obtain the accurate energy. Calculated results demonstrate that the electrophilic substitutions of nitronium ions from the nitration reagents and the abstractions of protons in the complex intermediates are the main formation mechanism of DNFO. BF4- is shown to be a better proton abstracter than HNO3 and H2O due to its no barrier combination with H+. The abstraction of proton by HNO3 is predicted to be more feasible than H2O because it can supply the nitration attacker (NO2+) and release more heat. Chloroform is a feasible solvent and heating properly is necessary for the two reactions due to the relatively high barrier of 37 kcal/mol. These conclusions provide some significant indications on the new experimental synthesis of DNFO.

  16. Formation of Lactic Acid from Cellulosic Biomass by Alkaline Hydrothermal Reaction

    NASA Astrophysics Data System (ADS)

    Yan, X.; Jini, F.; Kishita, A.; Enomoto, H.; Tohji, K.

    2008-02-01

    Glucose, as a model compound of cellulosic biomass, was used as a test material. Ca(OH)2 and NaOH were selected as alkali. Results showed that both NaOH and Ca(OH)2, can promote the formation of lactic acid in a hydrothermal reaction of glucose. In the case of the addition of NaOH, lactic acid was obtained with a good yield of 27% based on a carbon base at 300 °C for 60 s with a NaOH concentration of 2.5 M. In the case of the addition of Ca(OH)2, the highest yield of lactic acid is 20%, which occurred at 300 °C for 60 s with a Ca(OH)2 concentration of 0.32 M. The formation mechanisms of lactic acid from glucose were also discussed according to intermediate products identified. Lactic acid may be generated via formaldehyde, glycolaldehyde besides via the aldose having three carbon atoms in hydrothermal reaction which all formed by the reverse aldol condensation of hexoses.

  17. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    NASA Technical Reports Server (NTRS)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  18. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    SciTech Connect

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly

  19. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    DOE PAGESBeta

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) bothmore » significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the

  20. Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones

    SciTech Connect

    Jalan, Amrit; Allen, Joshua W.; Green, William H.

    2013-08-08

    Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

  1. Commitment, Compliance and Comfort Zones: The Effects of Formative Assessment on Vocational Education Students' Learning Careers

    ERIC Educational Resources Information Center

    Ecclestone, Kathryn

    2007-01-01

    Research evidence that well-executed formative assessment raises achievement and enhances motivation and autonomy has influenced policy and practice in schools and universities in the United Kingdom. Formative assessment is also built into the aims and assessment activities of outcome-based qualifications in post-compulsory education. Behind these…

  2. Unified reaction pathways for the prebiotic formation of RNA and DNA nucleobases.

    PubMed

    Jeilani, Yassin Aweis; Williams, Phoenix N; Walton, Sofia; Nguyen, Minh Tho

    2016-07-27

    The reaction pathways for the prebiotic formation of nucleobases are complex and lead to the formation of a mixture of products. In the past 50 years, there has been a concerted effort for identifying a unified mechanism for the abiotic origin of the biomolecules but with little success. In the present theoretical study, we identified two prominent precursors for the building up of RNA and DNA nucleobases under prebiotic conditions: (a) 1,2-diaminomaleonitrile (DAMN), which is a tetramer of hydrogen cyanide (HCN), and (b) formamide, a hydrolysis product of HCN; it is important to emphasize that HCN is the source of both precursors. We find that free radical pathways are potentially appropriate to account for the origin of nucleobases from HCN. The current study unites the formamide pathways with the DAMN pathways. The mechanisms for the formation of the RNA and DNA nucleobases (uracil, adenine, purine, cytosine) were studied by quantum chemical computations using density functional theory at the B3LYP/6-311G(d,p) level. All the routes involved proceed with relatively low energy barriers (within the error margin of DFT methods). We showed that the radical mechanisms for the formation of nucleobases could be unified through common precursors. The results demonstrated that 4-aminoimidazole-5-carbonitrile (AICN), which is a known precursor for nucleobases, is a product of DAMN. The overall mechanisms are internally consistent with the abiotic formation of the nucleobases, namely (a) under a meteoritic impact scenario on the early Earth's surface that generated high internal energy, and/or (b) in the (gas phase) interstellar regions without the presence of catalysts. PMID:27220279

  3. Formation of the giant Shakhdara migmatitic gneiss dome, Pamir, India-Asia collision zone

    NASA Astrophysics Data System (ADS)

    Stübner, Konstanze; Ratschbacher, Lothar; Hacker, Bradley; Dunkl, István; Gloaguen, Richard

    2013-04-01

    Cenozoic gneiss domes comprise one third of the surface exposure of the Pamir Mountains and provide a window into deep crustal processes of the India-Asia collision. The largest of these is the 350 × 90 km Shakhdara-Alichur composite dome of the southern Pamir, Tajikistan and Afghanistan. The Shakhdara and Alichur domes formed by footwall exhumation of two low-angle detachments: In the larger Shakhdara dome the top-to-S South Pamir shear zone (SPSZ) exhumed crust from 30-40 km depth; in the Alichur dome the top-to-N Alichur shear zone exhumed upper crustal rocks. The subdomes are separated by a low-strain horst. Non-coaxial shear in the Shakhdara dome is pervasive over the ~4 km thick SPSZ. The top of the shear zone is preserved at mountain peaks, the base is incised by the Panj gorge, which exposes the 'core' of the dome; total erosion is less than 4 km throughout most of the dome. We use a comprehensive geo-thermochronologic dataset of titanite, monazite, and zircon U/Th-Pb, mica Rb-Sr and 40Ar/39Ar, zircon and apatite fission track, and zircon (U-Th)/He ages to constrain the exhumation history of the southern Pamir domes. Doming started at ~21 Ma by crustal buckling and activation of a top-to-N normal shear zone (Gunt shear zone) along the northern rim of the Shakhdara dome, resulting in exhumation and cooling. The bulk of the exhumation was accomplished by northward extrusion of the SPSZ footwall, which was active from ~18-15 Ma to ~2 Ma; exhumation rates were 1-3 mm/yr. Erosion rates during and after the end of doming were 0.3-0.5 mm/yr within the domes and 0.1-0.3 mm/yr in the horst and in the SE Pamir plateau; incision rates of the major drainages were up to 1.0 mm/yr. Doming by footwall exhumation of the SPSZ resulted in up to 90 km N-S extension, coeval with ongoing N-S convergence between India and Asia. Extension opposes shortening along and above the reactivated Rushan-Pshart suture zone, a wide fold-thrust belt north of the Shakhdara-Alichur domes

  4. [The main radionuclides and dose formation in fish of the Chernobyl NPP exclusion zone].

    PubMed

    Gudkov, D I; Kaglian, A E; Kireev, S I; Nazarov, A B; Klenus, V G

    2008-01-01

    The results of the researches of spices-specificity, accumulation dynamics and distribution of 90Sr, of 137Cs and of transuranic elements in fish of the Chernobyl NPP exclusion zone are analysed. The data of estimations of absorbed doze rate from incorporated radionuclides for pray fish and predatory species are given. For the fish from the lake of the left-bank floodplain of the Pripyat River the increase of 90Sr specific activity is registered which is presumably connected with the dynamics of the physical-chemical forms of the radionuclide in soils and their wash out in water bodies from the catchment basin. Now about 90% of internal dose rate of fish from closed aquatic ecosystems within the Chernobyl NPP exclusion zone is caused by 90Sr incorporation. PMID:18666579

  5. Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

    1997-01-01

    Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

  6. Isotachophoretic zone formation of serum albumin in different free fluid electrophoresis instruments.

    PubMed

    Thormann, W; Firestone, M A; Sloan, J E; Long, T D; Mosher, R A

    1990-04-01

    The isotachophoretic behavior of a model protein, serum albumin, was examined (i) by computer simulation, (ii) by capillary isotachophoresis in HPE 100 and Tachophor 2127, (iii) by continuous flow isotachophoresis in Elphor VaP 22 and the BIO-STREAM Separator and (iv) by recycling isotachophoresis in an apparatus of our own design. Variations in monitored zone shapes can be explained by differences in engineering aspects and fluid stabilization principles of the instruments. PMID:2340824

  7. Formation of porous surface layers in reaction bonded silicon nitride during processing

    NASA Technical Reports Server (NTRS)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    An effort was undertaken to determine if the formation of the generally observed layer of large porosity adjacent to the as-nitride surfaces of reaction bonded silicon nitrides could be prevented during processing. Isostatically pressed test bars were prepared from wet vibratory milled Si powder. Sintering and nitriding were each done under three different conditions:(1) bars directly exposed to the furnance atmosphere; (2) bars packed in Si powder; (3) bars packed in Si3N4 powder. Packing the bars in either Si of Si3N4 powder during sintering retarded formation of the layer of large porosity. Only packing the bars in Si prevented formation of the layer during nitridation. The strongest bars (316 MPa) were those sintered in Si and nitrided in Si3N4 despite their having a layer of large surface porosity; failure initiated at very large pores and inclusions. The alpha/beta ratio was found to be directly proportional to the oxygen content; a possible explanation for this relationship is discussed.

  8. Levoglucosan formation from crystalline cellulose: importance of a hydrogen bonding network in the reaction.

    PubMed

    Hosoya, Takashi; Sakaki, Shigeyoshi

    2013-12-01

    Levoglucosan (1,6-anhydro-β-D-glucopyranose) formation by the thermal degradation of native cellulose was investigated by MP4(SDQ)//DFT(B3LYP) and DFT(M06-2X)//DFT(B3LYP) level computations. The computational results of dimer models lead to the conclusion that the degradation occurs by a concerted mechanism similar to the degradation of methyl β-D-glucoside reported in our previous study. One-chain models of glucose hexamer, in which the interchain hydrogen bonds of real cellulose crystals are absent, do not exhibit the correct reaction behavior of levoglucosan formation; for instance, the activation enthalpy (Ea =≈38 kcal mol(-1) ) is considerably underestimated compared to the experimental value (48-60 kcal mol(-1) ). This problem is solved with the use of two-chain models that contain interchain hydrogen bonds. The theoretical study of this model clearly shows that the degradation of the internal glucosyl residue leads to the formation of a levoglucosan precursor at the chain end and levoglucosan is selectively formed from this levoglucosan end. The calculated Ea (56-62 kcal mol(-1) ) agrees well with the experimental value. The computational results of three-chain models indicate that this degradation occurs selectively on the crystalline surface. All these computational results provide a comprehensive understanding of several experimental facts, the mechanisms of which have not yet been elucidated. PMID:24243863

  9. Density functional computational studies on the glucose and glycine Maillard reaction: Formation of the Amadori rearrangement products

    NASA Astrophysics Data System (ADS)

    Jalbout, Abraham F.; Roy, Amlan K.; Shipar, Abul Haider; Ahmed, M. Samsuddin

    Theoretical energy changes of various intermediates leading to the formation of the Amadori rearrangement products (ARPs) under different mechanistic assumptions have been calculated, by using open chain glucose (O-Glu)/closed chain glucose (A-Glu and B-Glu) and glycine (Gly) as a model for the Maillard reaction. Density functional theory (DFT) computations have been applied on the proposed mechanisms under different pH conditions. Thus, the possibility of the formation of different compounds and electronic energy changes for different steps in the proposed mechanisms has been evaluated. B-Glu has been found to be more efficient than A-Glu, and A-Glu has been found more efficient than O-Glu in the reaction. The reaction under basic condition is the most favorable for the formation of ARPs. Other reaction pathways have been computed and discussed in this work.0

  10. Break up of the lithosphere and the formation of the sedimentary basins in the Eurasia-Pacific transition zone

    NASA Astrophysics Data System (ADS)

    Rodnikov, A. G.; Sergeyeva, N. A.; Zabarinskaya, L. P.

    2009-04-01

    The studies of the deep structure of the sedimentary basins were carried out in the frame of the international Geotraverse Project from deep sections of the tectonosphere including the lithosphere and asthenosphere on the basis of combined interpretation of geological and geophysical data. Research subjects are the sedimentary basins of the transition zone from Eurasian continent to the Pacific such as Northern Sakhalin basin, Deryugin basin and Tatar strait trough in the Sea of Okhotsk and sedimentary basins of the North China Plain and Philippine Sea. It was established that the formation of sedimentary basins is associated with the processes going on in the Earth's interior specifically in the asthenosphere. The asthenosphere occurs at depth of 50 - 80 km under the old Paleogene basisns and at depth of around 30 km under the Neogene basins. Under the Pliocene-Quaternary inter-arc basins the asthenosphere occurs at depth of 10-20-km. Upwelling of the hot asthenosphere to the crust caused the break-up of the lithosphere, the formation of rifts, basalt magma eruption, and hydrothermal activity. Sedimentary basins are related to ancient and recent subduction zones. They are distinguished for their anomalous deep structure. Their features are rift structures or spreading centers in their basement; active magmatism at the initial stage of formation; hydrothermal processes associated with sulfides formation; high density of the heat flow; the location of the asthenospheric diapirs beneath sedimentary basins. Asthenospheric diapirs are the source of fluids and heat. Mantle fluids comprise both gaseous and liquid hydrocarbons. The asthenospheric diapirs are likely to be channels by which hot mantle fluids penetrate into sedimentary basins, thus providing organic matter transformation and being an additional source of hydrocarbons.

  11. Secondary Organic Aerosol Formation in Aerosol Water by Photochemical Reactions of Gaseous Mixture of Monoterpene and Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Lim, H.; Yi, S.; Park, J.; Cho, H.; Jung, K.

    2011-12-01

    There exist large uncertainties in model predictions for climate change and regional air quality. It could be caused by incomplete integration of secondary organic aerosol (SOA) formation in atmospheric chemical models. Recent laboratory studies have found SOA formation through chemical reactions on aerosol surface and in aerosol water. Water soluble organics formed by photochemical degradation of biogenic organics including isoprene and anthropogenic aromatics are predicted to form substantial amount of SOA through the newly found pathways. Although SOA formation in bulk aqueous solution was reported for laboratory experiments of various precursors (e.g., water soluble carbonyls and phenols), little is known for SOA formation in real aerosol water. In this study, photochemical reactions of the gaseous mixture of monoterpene and hydrogen peroxide were examined to investigate SOA formation through reactions in real aerosol phase water. SOA formation was conducted using a flow tube reactor (ID 30 cm x L 150 cm, FEP) and a smog chamber using FEP film in the presence of dry and wet seed particles. Acidity and chemical composition of seed aerosol were also controlled as important parameters influencing SOA formation. Particle size distribution and aerosol composition were analyzed to account for differences in SOA formation mechanisms and yields for dry and wet particles. The differences might be mainly associated with SOA formation in aerosol phase water. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-0000221).

  12. In-situ formation of Indian Mantle in global subduction zones

    NASA Astrophysics Data System (ADS)

    Nebel, Oliver; Arculus, Richard; Davies, Rhodri

    2014-05-01

    The isotopic signatures of Sr-Nd-Pb-Hf-Os in mid-ocean ridge basalts (MORB) in the Indian Ocean are clearly distinct compared with their Atlantic/Pacific (A/P) counterparts. The origin of this isotopic distinction has been a matter of debate since its discovery by Dupré and Allègre (1983). Current models advocate: (i) delamination of ancient, negatively buoyant lower crust/lithosphere from a supercontinent; (ii) contamination of A/P-style mantle with plumes (the original association with the DUPAL anomaly); or (iii) long-term overprint by a subduction component (SC) surrounding a former supercontinent. The sum of various stable and radiogenic isotope proxies appears to support a delamination scenario, but alternatives, or the combination of the aforementioned scenarios, are possible. Irrespective of the origin of the Indian mantle domain, isotopic signatures similar to those of Indian MORB and hot-spots are observed in arc/back-arc systems associated with western Pacific subduction zones. These isotope signatures have been regarded as unequivocally derived from Indian-type mantle, and accordingly used to trace eastward flow of that type of mantle. Here we show the majority of igneous rocks associated with subduction zone systems mimic Indian-type mantle in Pb isotope space, but are distinct in Hf-Nd isotope co-variations. We suggest isotopic signatures believed to be derived from Indian mantle in subduction zones are the result of medium-term subduction overprint of evolving A/P-type mantle wedges. This feature results from the relative mobility of U-Pb>Sm-Nd>Lu-Hf in subducted slab-derived components and Th/U (k) fractionation in the mantle wedge. Elevation of k in the wedge from 2.6 (MORB) to about 6-12 can account for the shift in Pb isotope space over a duration of ca. 100-200 Myrs; "decoupling" of Hf-Nd isotopes reflect the subduction component vs mantle wedge contribution. More generally, "Pseudo-Indian mantle" is noted as common in subduction zones

  13. Time-dependent insulin oligomer reaction pathway prior to fibril formation: Cooling and seeding

    PubMed Central

    Sorci, Mirco; Grassucci, Robert A.; Hahn, Ingrid; Frank, Joachim; Belfort, Georges

    2009-01-01

    The difficulty in identifying the toxic agents in all amyloid-related diseases is likely due to the complicated kinetics and thermodynamics of the nucleation process and subsequent fibril formation. The slow progression of these diseases suggests that the formation, incorporation and/or action of toxic agents is possibly rate limiting. Candidate toxic agents include precursors (some at very low concentrations), also called oligomers and protofibrils, and the fibrils. Here, we investigate the kinetic and thermodynamic behavior of human insulin oligomers (imaged by cryo-EM) under fibril forming conditions (pH 1.6 and 65°C) by probing the reaction pathway to insulin fibril formation using two different types of experiments – cooling and seeding – and confirm the validity of the nucleation model and its effect on fibril growth. The results from both the cooling and seeding studies confirm the existence of a time-changing oligomer reaction process prior to fibril formation that likely involves a rate-limiting nucleation process followed by structural rearrangements of intermediates (into β-sheet rich entities) to form oligomers that then form fibrils. The latter structural rearrangement step occurs even in the absence of nuclei (i.e. with added heterologous seeds). Nuclei are formed at the fibrillation conditions (pH 1.6 and 65°C) but are also continuously formed during cooling at pH 1.6 and 25°C. Within the time-scale of the experiments, only after increasing the temperature to 65°C are the trapped insulin nuclei and resultant structures able to induce the structural rearrangement step and overcome the energy barrier to form fibrils. This delay in fibrillation and accumulation of nuclei at low temperature (25°C), result in a decrease in the mean length of the fibers when placed at 65°C. Fits of an empirical model to the data provide quantitative measures of the delay in the lag-time during the nucleation process and subsequent reduction in fibril growth rate

  14. Concurrent Formation of Carbon-Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction.

    PubMed

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C-H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C-C bond formation via C-H transformation and production of functionalized graphene. PMID:27181191

  15. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    NASA Astrophysics Data System (ADS)

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-05-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene.

  16. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    PubMed Central

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene. PMID:27181191

  17. Origin of the synchronicity in bond formation in polar Diels-Alder reactions: an ELF analysis of the reaction between cyclopentadiene and tetracyanoethylene.

    PubMed

    Domingo, Luis R; Pérez, Patricia; Sáez, Jose A

    2012-05-21

    The origin of the synchronicity in C-C bond formation in polar Diels-Alder (P-DA) reactions involving symmetrically substituted electrophilic ethylenes has been studied by an ELF analysis of the electron reorganization along the P-DA reaction of cyclopentadiene (Cp) with tetracyanoethylene (TCE) at the B3LYP/6-31G* level. The present study makes it possible to establish that the synchronicity in C-C bond formation in P-DA reactions is controlled by the symmetric distribution of the electron-density excess reached in the electrophile through the charge transfer process, which can be anticipated by an analysis of the spin electron-density at the corresponding radical anion. The ELF comparative analysis of bonding along the DA reactions of Cp with ethylene and with TCE asserts that these DA reactions, which have a symmetric electron reorganization, do not have a cyclic electron reorganization as the pericyclic mechanism states. Due to the very limited number of cases of symmetrically substituted ethylenes, we can conclude that the synchronous mechanism is an exception of DA reactions. PMID:22527420

  18. Chemical pattern formation driven by a neutralization reaction. I. Mechanism and basic features

    NASA Astrophysics Data System (ADS)

    Eckert, Kerstin; Acker, Margret; Shi, Ying

    2004-02-01

    We study the chemohydrodynamic pattern formation during interfacial mass transfer accompanied by a neutralization reaction. The system, which is placed in a Hele-Shaw cell, is a configuration of two immiscible liquid phases in contact along a plane interface. In the upper, organic layer a carboxylic acid is dissolved, the concentration of which is far beyond the equilibrium partition ratio. Interfacial acid transfer initiates the neutralization with an organic base dissolved in the lower, aqueous layer. Focus is on the exploration of a novel instability consisting of a regular cellular structure penetrating into the aqueous bulk solution. By several complementary experimental methods, including shadowgraph visualization with different magnifications, particle image velocimetry, differential interferometry, and detailed measurements of relevant material properties, the driving mechanism of the instability is identified. Synthesis of the experimental results suggests that lateral differences in buoyancy are responsible for the convection.

  19. Formation of porous surface layers in reaction bonded silicon nitride during processing

    NASA Technical Reports Server (NTRS)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

  20. Uranyl triazolate formation via an in situ Huisgen 1,3-dipolar cycloaddition reaction

    SciTech Connect

    Knope, Karah E.; Cahill, Christopher L.

    2010-08-27

    A two dimensional UO22+ coordination polymer, (UO2)3(C10H5N3O4)2(OH)2(H2O)2, has been synthesized under solvothermal conditions. The triazolate ligand, 1-(4-carboxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid (CPTAZ) has been generated via a 1,3-dipolar cycloaddition of 4-azidobenzoic acid and propiolic acid. Reactions of the UO22+ cation with both the in situ generated triazolate ligand and the presynthesized ligand have been explored. The structure, fluorescent and thermal behaviour of this material are presented, as is a discussion of the utility of in situ ligand formation versus direct assembly.

  1. Magma reservoirs and neutral buoyancy zones on Venus - Implications for the formation and evolution of volcanic landforms

    NASA Astrophysics Data System (ADS)

    Head, James W.; Wilson, Lionel

    1992-03-01

    The production of magma reservoirs and neutral buoyancy zones (NBZs) on Venus and the implications of their development for the formation and evolution of volcanic landforms are examined. The high atmospheric pressure on Venus reduces volatile exsolution and generally serves to inhibit the formation of NBZs and shallow magma reservoirs. For a range of common terrestrial magma-volatile contents, magma ascending and erupting near or below mean planetary radius (MPR) should not stall at shallow magma reservoirs; such eruptions are characterized by relatively high total volumes and effusion rates. For the same range of volatile contents at 2 km above MPR, about half of the cases result in the direct ascent of magma to the surface and half in the production of neutral buoyancy zones. NBZs and shallow magma reservoirs begin to appear as gas content increases and are nominally shallower on Venus than on earth. For a fixed volatile content, NBZs become deeper with increasing elevation: over the range of elevations treated in this study (-1 km to +4.4 km) depths differ by a factor of 2-4. Factors that may account for the low height of volcanoes on Venus are discussed.

  2. Magma reservoirs and neutral buoyancy zones on Venus - Implications for the formation and evolution of volcanic landforms

    NASA Technical Reports Server (NTRS)

    Head, James W.; Wilson, Lionel

    1992-01-01

    The production of magma reservoirs and neutral buoyancy zones (NBZs) on Venus and the implications of their development for the formation and evolution of volcanic landforms are examined. The high atmospheric pressure on Venus reduces volatile exsolution and generally serves to inhibit the formation of NBZs and shallow magma reservoirs. For a range of common terrestrial magma-volatile contents, magma ascending and erupting near or below mean planetary radius (MPR) should not stall at shallow magma reservoirs; such eruptions are characterized by relatively high total volumes and effusion rates. For the same range of volatile contents at 2 km above MPR, about half of the cases result in the direct ascent of magma to the surface and half in the production of neutral buoyancy zones. NBZs and shallow magma reservoirs begin to appear as gas content increases and are nominally shallower on Venus than on earth. For a fixed volatile content, NBZs become deeper with increasing elevation: over the range of elevations treated in this study (-1 km to +4.4 km) depths differ by a factor of 2-4. Factors that may account for the low height of volcanoes on Venus are discussed.

  3. A Macroscopic Reaction: Direct Covalent Bond Formation between Materials Using a Suzuki-Miyaura Cross-Coupling Reaction

    NASA Astrophysics Data System (ADS)

    Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira

    2014-09-01

    Cross-coupling reactions are important to form C-C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively.

  4. A Macroscopic Reaction: Direct Covalent Bond Formation between Materials Using a Suzuki-Miyaura Cross-Coupling Reaction

    PubMed Central

    Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira

    2014-01-01

    Cross-coupling reactions are important to form C–C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively. PMID:25231557

  5. Formation of photosystem II reaction centers that work as energy sinks in lichen symbiotic Trebouxiophyceae microalgae.

    PubMed

    Guéra, Alfredo; Gasulla, Francisco; Barreno, Eva

    2016-04-01

    Lichens are poikilohydric symbiotic organisms that can survive in the absence of water. Photosynthesis must be highly regulated in these organisms, which live under continuous desiccation-rehydration cycles, to avoid photooxidative damage. Analysis of chlorophyll a fluorescence induction curves in the lichen microalgae of the Trebouxiophyceae Asterochloris erici and in Trebouxia jamesii (TR1) and Trebouxia sp. (TR9) phycobionts, isolated from the lichen Ramalina farinacea, shows differences with higher plants. In the presence of the photosynthetic electron transport inhibitor DCMU, the kinetics of Q(A) reduction is related to variable fluorescence by a sigmoidal function that approaches a horizontal asymptote. An excellent fit to these curves was obtained by applying a model based on the following assumptions: (1) after closure, the reaction centers (RCs) can be converted into "energy sink" centers (sRCs); (2) the probability of energy leaving the sRCs is very low or zero and (3) energy is not transferred from the antenna of PSII units with sRCs to other PSII units. The formation of sRCs units is also induced by repetitive light saturating pulses or at the transition from dark to light and probably requires the accumulation of reduced Q(A), as well as structural changes in the reaction centers of PSII. This type of energy sink would provide a very efficient way to protect symbiotic microalgae against abrupt changes in light intensity. PMID:26482588

  6. Formation of cysteine-S-conjugates in the Maillard reaction of cysteine and xylose.

    PubMed

    Cerny, Christoph; Guntz-Dubini, Renée

    2013-11-15

    Cysteine-S-conjugates (CS-conjugates) occur in foods derived from plant sources like grape, passion fruit, onion, garlic, bell pepper and hops. During eating CS-conjugates are degraded into aroma-active thiols by β-lyases that originate from oral microflora. The present study provides evidence for the formation of the CS-conjugates S-furfuryl-l-cysteine (FFT-S-Cys) and S-(2-methyl-3-furyl)-l-cysteine (MFT-S-Cys) in the Maillard reaction of xylose with cysteine at 100°C for 2h. The CS-conjugates were isolated using cationic exchange and reversed-phase chromatography and identified by (1)H NMR, (13)C NMR and LC-MS(2). Spectra and LC retention times matched those of authentic standards. To the best of our knowledge, this is the first time that CS-conjugates are described as Maillard reaction products. Furfuryl alcohol (FFA) is proposed as an intermediate which undergoes a nucleophilic substitution with cysteine. Both FFT-S-Cys and MFT-S-Cys are odourless but produce strong aroma when tasted in aqueous solutions, supposedly induced by β -lyases from the oral microflora. The perceived aromas resemble those of the corresponding aroma-active thiols 2-furfurylthiol (FFT) and 2-methyl-3-furanthiol (MFT) which smell coffee-like and meaty, respectively. PMID:23790889

  7. Mount St. Augustine volcano fumarole wall rock alteration: mineralogy, zoning, composition and numerical models of its formation process

    NASA Astrophysics Data System (ADS)

    Getahun, Aberra; Reed, Mark H.; Symonds, Robert

    1996-05-01

    Intensely altered wall rock was collected from high-temperature (640 °C) and low-temperature (375 °C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl 3) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375 °C; (b) cooling of the 1987 gas from 870 to 100 °C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100 °C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640 °C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375 °C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides

  8. Condensation Reactions and Formation of Amides, Esters, and Nitriles Under Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Rushdi, Ahmed I.; Simoneit, Bernd R. T.

    2004-06-01

    Hydrothermal pyrolysis experiments were performed to assess condensation (dehydration) reactions to amide, ester, and nitrile functionalities from lipid precursors. Beside product formation, organic compound alteration and stability were also evaluated. Mixtures of nonadecanoic acid, hexadecanedioic acid, or hexadecanamide with water, ammonium bicarbonate, and oxalic acid were heated at 300°C for 72 h. In addition, mixtures of ammonium bicarbonate and oxalic acid solutions were used to test the abiotic formation of organic nitrogen compounds at the same temperature. The resulting products were condensation compounds such as amides, nitriles, and minor quantities of N-methylalkyl amides, alkanols, and esters. Mixtures of alkyl amide in water or oxalic acid yielded mainly hydrolysis and dehydration products, and with ammonium bicarbonate and oxalic acid the yield of condensation products was enhanced. The synthesis experiments with oxalic acid and ammonium bicarbonate solutions yielded homologous series of alkyl amides, alkyl amines, alkanes, and alkanoic acids, all with no carbon number predominances. These organic nitrogen compounds are stable and survive under the elevated temperatures of hydrothermal fluids.

  9. Formation of carriers in Ti-oxide thin films by substitution reactions

    SciTech Connect

    Liu, Y. S.; Lin, Y. H.; Wei, Y. S.; Liu, C. Y.

    2012-02-15

    Conductive Ti-oxide thin films are produced using a reactive sputtering and post-annealing process. The lowest resistivity of Ti-oxide thin films (2.30 x 10{sup -2}{Omega}-cm) can be achieved after annealing for 1 h at 400 deg. C in ambient O{sub 2}. Additionally, the Hall measurement results indicate that the carrier concentration increases during the initial 1-h annealing process before decreasing during subsequent annealing. By curve fitting the O{sub ls} core-level peaks in the x ray photoelectron spectroscopy (XPS) spectrum of the annealed Ti-oxide thin films, we found that the oxygen (O) vacancy concentration monotonically increases with annealing time, which differs from the behavior of the carrier concentration regarding annealing time. This means that the O-vacancy mechanism alone cannot explain the formation of carriers in Ti-oxide thin films. By curve-fitting core-level Ti peaks in the XPS spectrum of annealed Ti-oxide thin films, a Ti{sup 3+}-to-Ti{sup 4+} substitution reaction in the TiO{sub 2} phase of the Ti-oxide thin film after annealing plays the dominant role in the formation of conduction carriers. Instead of the O-vacancy mechanism, the Ti{sup 3+}-to-Ti{sup 4+} substitution mechanism can explain the concentration of carriers in Ti-oxide thin films following annealing.

  10. Intramolecular condensation reactions of {alpha}, {omega}- bis(triethoxy-silyl)alkanes. Formation of cyclic disilsesquioxanes

    SciTech Connect

    Loy, D.A.; Carpenter, J.P.; Myers, S.A.; Assink, R.A.; Small, J.H.; Greaves, J.; Shea, K.J.

    1996-08-01

    Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane (1) and 1,4-bis(triethoxysilyl)butane (2) were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed withe the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to perserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.

  11. Formation of Complex Organics by Gas Phase and Intracluster Ion-Molecule Reactions Involving Acetylene and Hydrogen Cyanide

    NASA Astrophysics Data System (ADS)

    El-Shall, S.; Hamed, A.; Soliman, A. R.; Momoh, P. O.

    2011-05-01

    Many complex organics including polycyclic aromatic hydrocarbons are present in flames and combustion processes as well as in interstellar clouds and solar nebulae. Here, we present evidence for the formation of complex covalent organics by gas phase and intracluster reactions of the benzene, phenylium, pyridine, pyrimidine, phenylacetylene and benzonitrile cations with acetylene and hydrogen cyanide molecules. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. Measurements of collision cross sections in helium provide structural information on the adducts and allow probing structural changes at different temperatures (isomerization). We observed multiple additions of five acetylene molecules on the pyridine cation at room temperature. This is a remarkable result considering that only two acetylene molecules were added to the phenyl cation and no addition was observed on the benzene cation at room temperature. The experimental results are in full agreement with the ab initio calculations which predict that the first and second acetylenes add to the pyridine ion in barrierless, highly exothermic reactions. Similar reactions have been observed for the pyrimidine radical cation although the extent of the addition reactions is limited to only two acetylene molecules at room temperature. The results provide the first evidence for the incorporation of nitrogen in the formation cyclic hydrocarbons via the gas phase reactions of pyridine and pyrimidine ions with acetylene molecules. In addition, the formation of covalent adducts in the ionized acetylene/HCN system will be reported for the first time. Sequential reactions leading to the formation of pyridine and pyrimidine radical cations and higher adducts are observed over a wide range of temperature and pressure. The formation of these covalent adducts may represent a general class of addition reactions that can form complex

  12. Severe inflammatory reaction induced by peritoneal trauma is the key driving mechanism of postoperative adhesion formation

    PubMed Central

    2011-01-01

    Background Many factors have been put forward as a driving mechanism of surgery-triggered adhesion formation (AF). In this study, we underline the key role of specific surgical trauma related with open surgery (OS) and laparoscopic (LS) conditions in postoperative AF and we aimed to study peritoneal tissue inflammatory reaction (TIR), remodelling specific complications of open surgery (OS) versus LS and subsequently evaluating AF induced by these conditions. Methods A prospective randomized study was done in 80 anaesthetised female Wistar rats divided equally into 2 groups. Specific traumatic OS conditions were induced by midline incision line (MIL) extension and tissue drying and specific LS conditions were remodelled by intraperitoneal CO2 insufflation at the 10 cm of water. TIR was evaluated at the 24th, 72nd, 120th and 168th hour by scoring scale. Statistical analysis was performed by the non-parametric t test and two-way ANOVA using Bonferroni post-tests. Results More pronounced residual TIR was registered after OS than after LS. There were no significant TIR interactions though highly significant differences were observed between the OS and LS groups (p < 0.0001) with regard to surgical and time factors. The TIR change differences between the OS and LS groups were pronounced with postoperative time p < 0.05 at the 24th and 72nd; p < 0.01 - 120th and p < 0.001 - 168th hrs. Adhesion free wounds were observed in 20.0 and 31.0% of cases after creation of OS and LS conditions respectively; with no significant differences between these values (p > 0.05). However larger adhesion size (41.67 ± 33.63) was observed after OS in comparison with LS (20.31 ± 16.38). The upper-lower 95% confidential limits ranged from 60.29 to 23.04 and from 29.04 to 11.59 respectively after OS and LS groups with significant differences (p = 0.03). Analogous changes were observed in adhesion severity values. Subsequently, severe TIR parameters were followed by larger sizes of severe

  13. Contrasts in Sea Ice Formation and Production in the Arctic Seasonal and Perennial Ice Zones

    NASA Technical Reports Server (NTRS)

    Kwok, R.

    2006-01-01

    Four years (1997-2000) of RADARSAT Geophysical Processor System (RGPS) data are used to contrast the sea ice deformation and production regionally, and in the seasonal (SIZ) and perennial (PIZ) ice zones. Ice production is of seasonal ice in openings during the winter. 3-day estimates of these quantities are provided within Lagrangian elements initially 10 km on a side. A distinct seasonal cycle is seen in both zones with these estimates highest in the late fall and with seasonal minimums in the mid-winter. Regional divergence over the winter could be up to 30%. Spatially, the highest deformation is in the SIZ north of coastal Alaska. Both ice deformation and production are higher in the SIZ: deformation-related ice production in the SIZ (approx.0.5 m) is 1.5-2.3 times that of the PIZ (approx.0.3 m) - this is connected to ice strength and thickness. Atmospheric forcing and boundary layer structure contribute to only the seasonal and interannual variability. Seasonal ice growth in ice fractures accounts for approx.25-40% of the total ice production of the Arctic Ocean. By itself, this deformation-ice production relationship could be considered a negative feedback when thickness is perturbed. However, the overall effect on ice production in the face of increasing seasonal and thinner/weaker ice coverage could be modified by: local destabilization of the water column promoting overturning of warmer water due to increased brine rejection; and, the upwelling of the pynocline associated with increased occurrence of large shear motion in sea ice.

  14. Formation of plagioclase-bearing peridotite and a peridotite-wehrlite-gabbro suite through melt-rock reaction: An experimental study

    NASA Astrophysics Data System (ADS)

    Saper, L.; Liang, Y.

    2012-12-01

    Plagioclase-bearing peridotites are observed among abyssal peridotites, massif peridotites, and mantle sections of ophiolites of lherzolite subtype. Formation of plagioclase-bearing peridotites is often attributed to basalt impregnation into host harzburgite or lherzolite in a thermal boundary layer. During transport through asthenospheric mantle, melt generated in the deep mantle will inevitably interact with the overlying mantle column through reactive dissolution and may leave geochemical imprints on plagioclase-bearing peridotites. To assess the role of melt-rock reaction on the formation of plagioclase-bearing peridotites and its implications for lithosphere composition, we conducted dissolution experiments in which a 88% spinel lherzolite + 12% basalt starting mixture was juxtaposed against a primitive MORB in a graphite-lined molybdenum capsule. The reaction couples were run at 1300°C and 1 GPa for 1 or 24 hrs, and then stepped cooled to 1050°C and 0.7 GPa over the next several days. Cooling promotes in situ crystallization of interstitial melts, allowing us to better characterize the mineral compositional trends produced and observed by melt-rock reaction and crystallization. A gabbro and a plagioclase-bearing peridotite were observed in the two halves of the reaction couple after the experiments were completed. The peridotite from the 24 hr reaction experiment is mostly composed of subhedral to euhedral olivines (10-50 μm in size, Mg# 75-83), poikilitic clinopyroxene (~100 μm in size, Mg# 73-83) with olivine and spinel chadocrysts, and interstitial plagioclase (An# 68-78) and melt. In a control experiment quenched after a 24 hour reaction at 1300°C the basalt completely dissolved the pyroxenes and spinels leaving a residue of rounded olivine grains (10-100 μm in size) surrounded by a relatively large melt fraction. Textural results from the step-cooling experiments suggest the following crystallization sequence from the olivine+melt mush: olivine

  15. Mount St. Augustine volcano fumarole wall rock alteration: Mineralogy, zoning, composition and numerical models of its formation process

    USGS Publications Warehouse

    Getahun, A.; Reed, M.H.; Symonds, R.

    1996-01-01

    Intensely altered wall rock was collected from high-temperature (640??C) and low-temperature (375??C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl3) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375??C; (b) cooling of the 1987 gas from 870 to 100??C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100??C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640??C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375??C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides (magnetite

  16. Carbon dioxide sequestration via olivine carbonation: Examining the formation of reaction products

    NASA Astrophysics Data System (ADS)

    King, H. E.; Plümper, O.; Putnis, A.

    2009-04-01

    Due to its abundance and natural ability to sequester CO2, olivine has been proposed as one mineral that could be used in the control of CO2 emissions into the atmosphere (Metz, 2005). Large scale peridotite deposits found in locations such as the Western Gneiss Region in Norway could provide in-situ sites for sequestration or the raw materials for ex-situ mineral carbonation. Determining the conditions under which magnesite (MgCO3) forms most efficiently is crucial to conduct a cost effective process. Understanding the development of secondary minerals is particularly important for in-situ methods as these phases can form passivating layers and affect the host rock porosity. The final solution of flow-through experiments conducted at alkaline pH have been shown to be supersaturated with respect to talc and chrysotile (Giammer et al., 2005), although these phases were not found to have precipitated the formation of a passivating, amorphous silica layer has been observed on reacted olivine surfaces (Bearat et al., 2006). By studying magnesite and other products produced during the carbonation of olivine within Teflon lined steel autoclaves we have begun to form a more comprehensive understanding of how these reactions would proceed during sequestration processes. We have performed batch experiments using carbonated saline solutions in the presence of air or gaseous CO2 from 80 to 200 ˚ C. X-ray powder diffraction was used to identify magnesite within the reaction products. Crystals of magnesite up to 20 m in diameter can be observed on olivine grain surfaces with scanning electron microscopy. Secondary reaction products formed a platy layer on olivine surfaces in reactions above 160 ˚ C and below pH 12. Energy dispersive X-ray analysis of the platy layer revealed an increase in Fe concentration. The macroscopically observable red colouration of the reaction products and Raman spectroscopy indicate that hematite is present in these layers. For experiments with

  17. VALIDATION AND RESULTS OF A PSEUDO-MULTI-ZONE COMBUSTION TRAJECTORY PREDICTION MODEL FOR CAPTURING SOOT AND NOX FORMATION ON A MEDIUM DUTY DIESEL ENGINE

    SciTech Connect

    Bittle, Joshua A.; Gao, Zhiming; Jacobs, Timothy J.

    2013-01-01

    A pseudo-multi-zone phenomenological model has been created with the ultimate goal of supporting efforts to enable broader commercialization of low temperature combustion modes in diesel engines. The benefits of low temperature combustion are the simultaneous reduction in soot and nitric oxide emissions and increased engine efficiency if combustion is properly controlled. Determining what qualifies as low temperature combustion for any given engine can be difficult without expensive emissions analysis equipment. This determination can be made off-line using computer models or through factory calibration procedures. This process could potentially be simplified if a real-time prediction model could be implemented to run for any engine platform this is the motivation for this study. The major benefit of this model is the ability for it to predict the combustion trajectory, i.e. local temperature and equivalence ratio in the burning zones. The model successfully captures all the expected trends based on the experimental data and even highlights an opportunity for simply using the average reaction temperature and equivalence ratio as an indicator of emissions levels alone - without solving formation sub-models. This general type of modeling effort is not new, but a major effort was made to minimize the calculation duration to enable implementation as an input to real-time next-cycle engine controller Instead of simply using the predicted engine out soot and NOx levels, control decisions could be made based on the trajectory. This has the potential to save large amounts of calibration time because with minor tuning (the model has only one automatically determined constant) it is hoped that the control algorithm would be generally applicable.

  18. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-08-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

  19. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-03-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

  20. Immunomodulatory Gene Therapy Prevents Antibody Formation and Lethal Hypersensitivity Reactions in Murine Pompe Disease

    PubMed Central

    Sun, Baodong; Kulis, Michael D; Young, Sarah P; Hobeika, Amy C; Li, Songtao; Bird, Andrew; Zhang, Haoyue; Li, Yifan; Clay, Timothy M; Burks, Wesley; Kishnani, Priya S; Koeberl, Dwight D

    2009-01-01

    Infantile Pompe disease progresses to a lethal cardiomyopathy in absence of effective treatment. Enzyme-replacement therapy (ERT) with recombinant human acid α-glucosidase (rhGAA) has been effective in most patients with Pompe disease, but efficacy was reduced by high-titer antibody responses. Immunomodulatory gene therapy with a low dose adeno-associated virus (AAV) vector (2 × 1010 particles) containing a liver-specific regulatory cassette significantly lowered immunoglobin G (IgG), IgG1, and IgE antibodies to GAA in Pompe disease mice, when compared with mock-treated mice (P < 0.05). AAV-LSPhGAApA had the same effect on GAA-antibody production whether it was given prior to, following, or simultaneously with the initial GAA injection. Mice given AAV-LSPhGAApA had significantly less decrease in body temperature (P < 0.001) and lower anaphylactic scores (P < 0.01) following the GAA challenge. Mouse mast cell protease-1 (MMCP-1) followed the pattern associated with hypersensitivity reactions (P < 0.05). Regulatory T cells (Treg) were demonstrated to play a role in the tolerance induced by gene therapy as depletion of Treg led to an increase in GAA-specific IgG (P < 0.001). Treg depleted mice were challenged with GAA and had significantly stronger allergic reactions than mice given gene therapy without subsequent Treg depletion (temperature: P < 0.01; symptoms: P < 0.05). Ubiquitous GAA expression failed to prevent antibody formation. Thus, immunomodulatory gene therapy could provide adjunctive therapy in lysosomal storage disorders treated by enzyme replacement. PMID:19690517

  1. Immunomodulatory gene therapy prevents antibody formation and lethal hypersensitivity reactions in murine pompe disease.

    PubMed

    Sun, Baodong; Kulis, Michael D; Young, Sarah P; Hobeika, Amy C; Li, Songtao; Bird, Andrew; Zhang, Haoyue; Li, Yifan; Clay, Timothy M; Burks, Wesley; Kishnani, Priya S; Koeberl, Dwight D

    2010-02-01

    Infantile Pompe disease progresses to a lethal cardiomyopathy in absence of effective treatment. Enzyme-replacement therapy (ERT) with recombinant human acid alpha-glucosidase (rhGAA) has been effective in most patients with Pompe disease, but efficacy was reduced by high-titer antibody responses. Immunomodulatory gene therapy with a low dose adeno-associated virus (AAV) vector (2 x 10(10) particles) containing a liver-specific regulatory cassette significantly lowered immunoglobin G (IgG), IgG1, and IgE antibodies to GAA in Pompe disease mice, when compared with mock-treated mice (P < 0.05). AAV-LSPhGAApA had the same effect on GAA-antibody production whether it was given prior to, following, or simultaneously with the initial GAA injection. Mice given AAV-LSPhGAApA had significantly less decrease in body temperature (P < 0.001) and lower anaphylactic scores (P < 0.01) following the GAA challenge. Mouse mast cell protease-1 (MMCP-1) followed the pattern associated with hypersensitivity reactions (P < 0.05). Regulatory T cells (Treg) were demonstrated to play a role in the tolerance induced by gene therapy as depletion of Treg led to an increase in GAA-specific IgG (P < 0.001). Treg depleted mice were challenged with GAA and had significantly stronger allergic reactions than mice given gene therapy without subsequent Treg depletion (temperature: P < 0.01; symptoms: P < 0.05). Ubiquitous GAA expression failed to prevent antibody formation. Thus, immunomodulatory gene therapy could provide adjunctive therapy in lysosomal storage disorders treated by enzyme replacement. PMID:19690517

  2. Dynamics of intraoceanic subduction initiation: 2. Suprasubduction zone ophiolite formation and metamorphic sole exhumation in context of absolute plate motions

    NASA Astrophysics Data System (ADS)

    van Hinsbergen, Douwe J. J.; Peters, Kalijn; Maffione, Marco; Spakman, Wim; Guilmette, Carl; Thieulot, Cedric; Plümper, Oliver; Gürer, Derya; Brouwer, Fraukje M.; Aldanmaz, Ercan; Kaymakcı, Nuretdin

    2015-06-01

    Analyzing subduction initiation is key for understanding the coupling between plate tectonics and the underlying mantle. Here we focus on suprasubduction zone (SSZ) ophiolites and how their formation links to intraoceanic subduction initiation in an absolute plate motion frame. SSZ ophiolites form the majority of exposed oceanic lithosphere fragments and are widely recognized to have formed during intraoceanic subduction initiation. Structural, petrological, geochemical, and plate kinematic constraints on their kinematic evolution show that SSZ crust forms at fore-arc spreading centers at the expense of a mantle wedge, thereby flattening the nascent slab. This leads to the typical inverted pressure gradients found in metamorphic soles that form at the subduction plate contact below and during SSZ crust crystallization. Former spreading centers are preserved in forearcs when subduction initiates along transform faults or off-ridge oceanic detachments. We show how these are reactivated when subduction initiates in the absolute plate motion direction of the inverting weakness zone. Upon inception of slab pull due to, e.g., eclogitization, the sole is separated from the slab, remains welded to the thinned overriding plate lithosphere, and can become intruded by mafic dikes upon asthenospheric influx into the mantle wedge. We propound that most ophiolites thus formed under special geodynamic circumstances and may not be representative of normal oceanic crust. Our study highlights how far-field geodynamic processes and absolute plate motions may force intraoceanic subduction initiation as key toward advancing our understanding of the entire plate tectonic cycle.

  3. Timing and mechanism of late-Pleistocene calcite vein formation across the Dead Sea Fault Zone, northern Israel

    NASA Astrophysics Data System (ADS)

    Nuriel, Perach; Weinberger, Ram; Rosenbaum, Gideon; Golding, Suzanne D.; Zhao, Jian-xin; Tonguc Uysal, I.; Bar-Matthews, Miryam; Gross, Michael R.

    2012-03-01

    The emplacement of calcite-filled veins perpendicular to the Dead Sea Fault Zone in northern Israel reflects strain partitioning during transpression. We present structural, geochemical, and U-Th geochronological data that constrain the mechanism, conditions and timing of vein formation. Vein walls are strongly brecciated and commonly cemented with coarsely crystalline calcite, whereas calcite-filled veins are composed of wall-parallel bands of calcite crystals. Elongated blocky and fibrous calcite crystals grew perpendicular to the vein walls and are characterised by a truncate sealing-hiatus morphology, indicating episodes of partial or complete sealing of the fractures during calcite precipitation. Stable isotope and rare-earth element and yttrium (REY) analyses indicate that calcite-filled veins precipitated by karst processes, involving meteoric water and limited fluid-rock interactions. U-Th dating results show a prolonged history of vein growth. While some veins initiated prior to 500 ka, the majority of the veins were active between 358 and 17 ka. Age constraints on vein activity correspond to an ˜E-W regional shortening phase in this sector of the Dead Sea Fault Zone, associated with an increased component of convergence during the late-Pleistocene.

  4. Aryl formate as bifunctional reagent: applications in palladium-catalyzed carbonylative coupling reactions using in situ generated CO.

    PubMed

    Li, Haoquan; Neumann, Helfried; Beller, Matthias; Wu, Xiao-Feng

    2014-03-17

    After decades of development, carbonylation reactions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functionalgroup tolerance and could be applied in carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. PMID:24677435

  5. Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

    PubMed

    Borrowman, Cuyler K; Zhou, Shouming; Burrow, Timothy E; Abbatt, Jonathan P D

    2016-01-01

    In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter. PMID:26603953

  6. The reaction mechanism of formation of chemically synthesized Nd{sub 2}Fe{sub 14}B hard magnetic nanoparticles

    SciTech Connect

    Deheri, P.K.; Shukla, S.; Ramanujan, R.V.

    2012-02-15

    Nd{sub 2}Fe{sub 14}B based magnetic materials exhibit excellent magnetic properties and are widely used in many engineering applications. However, chemical synthesis of this compound is challenging. In this work, the formation mechanism of chemically synthesized Nd{sub 2}Fe{sub 14}B magnetic nanoparticles was studied. Nd, Fe and B precursors were converted to Nd-Fe-B oxide by the sol-gel method, reduction of these oxides by CaH{sub 2} resulted in Nd{sub 2}Fe{sub 14}B nanoparticles. Nd{sub 2}Fe{sub 14}B phase formation resulted from two competing reactions: (a) Nd{sub 2}Fe{sub 14}B phase formation by direct combination of NdH{sub 2}, Fe and B, (b) Nd{sub 2}Fe{sub 17} phase formation from NdH{sub 2} and Fe, followed by Nd{sub 2}Fe{sub 14}B phase formation by the reaction of Nd{sub 2}Fe{sub 17} and B. Addition of boron to Nd-Fe-B oxide during reduction resulted in improved magnetic properties. The activation energy for Nd{sub 2}Fe{sub 14}B phase formation was found to be 365 kJ mol{sup -1}. The optimum heat treatment temperature and time for Nd{sub 2}Fe{sub 14}B phase formation were found to be 800 Degree-Sign C and 90 min, respectively. - Graphical abstract: The kinetics, reaction mechanism and morphology of Nd{sub 2}Fe{sub 14}B magnetic nanoparticles synthesized by sol-gel followed by reduction-diffusion at 800 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer The formation mechanism of Nd{sub 2}Fe{sub 14}B magnetic nanoparticles was studied. Black-Right-Pointing-Pointer Nd{sub 2}Fe{sub 14}B phase formation occurs by two parallel competing reactions. Black-Right-Pointing-Pointer Reaction of NdH{sub 2}, Fe and B resulted in Nd{sub 2}Fe{sub 14}B phase formation. Black-Right-Pointing-Pointer Nd{sub 2}Fe{sub 14}B phase can also be formed by the reaction of Nd{sub 2}Fe{sub 17} and B. Black-Right-Pointing-Pointer Maximum wt% of Nd{sub 2}Fe{sub 14}B phase was obtained at 800 Degree-Sign C and 90 min annealing.

  7. The BLADE-ON-PETIOLE genes are essential for abscission zone formation in Arabidopsis.

    PubMed

    McKim, Sarah M; Stenvik, Grethe-Elisabeth; Butenko, Melinka A; Kristiansen, Wenche; Cho, Sung Ki; Hepworth, Shelley R; Aalen, Reidunn B; Haughn, George W

    2008-04-01

    The Arabidopsis BLADE-ON-PETIOLE 1 (BOP1) and BOP2 genes encode redundant transcription factors that promote morphological asymmetry during leaf and floral development. Loss-of-function bop1 bop2 mutants display a range of developmental defects, including a loss of floral organ abscission. Abscission occurs along specialised cell files, called abscission zones (AZs) that develop at the junction between the leaving organ and main plant body. We have characterized the bop1 bop2 abscission phenotype to determine how BOP1 and BOP2 contribute to the known abscission developmental framework. Histological analysis and petal breakstrength measurements of bop1 bop2 flowers show no differentiation of floral AZs. Furthermore, vestigial cauline leaf AZs are also undifferentiated in bop1 bop2 mutants, suggesting that BOP proteins are essential to establish AZ cells in different tissues. In support of this hypothesis, BOP1/BOP2 activity is required for both premature floral organ abscission and the ectopic abscission of cauline leaves promoted by the INFLORESCENCE DEFICIENT IN ABSCISSION (IDA) gene under the control of the constitutive CaMV 35S promoter. Expression of several abscission-related marker genes, including IDA, is relatively unperturbed in bop1 bop2 mutants, indicating that these AZ genes respond to positional cues that are independent of BOP1/BOP2 activity. We also show that BOP1 and BOP2 promote growth of nectary glands, which normally develop at the receptacle adjacent to developing AZs. Taken together, these data suggest that BOP1/BOP2 activity is required for multiple cell differentiation events in the proximal regions of inflorescence lateral organs. PMID:18339677

  8. Photoinitiated electron-transfer reactions of aromatic imides with phenylcyclopropanes. Formation of radical ion pair cycloadducts. Mechanism of the reaction

    SciTech Connect

    Somich, C.; Mazzocchi, P.H.; Edwards, M.; Morgan, T.; Ammon, H.L. )

    1990-04-27

    Few investigations have addressed the cyclization of a radical anion-radical cation pair resulting from photoinitiated electron transfer. One system taht meets the criteria necessary to observe this phenomenon is the acceptor-donor pair N-methylphthalimide (NMP) and phenylcyclopropane (PC). Irradiation of NMP or N-methyl-2,3-naphthalimide (NMN) in the presence of PC in acetonitrile gave rise to two spiro tetrahydrofuranyl lactams. The regiochemistry and relative stereochemistry of these compounds were determined by NMR techniques and X-ray crystallography. The mechanism of the reaction proceeds via electron transfer from PC to the imide followed by coupling of the radical ion pair at the 1,2-position of the carbonyl to the cyclopropane ring in a stepwise fashion. Fluorescence quenching experiments, reaction efficiency, and the free energy for electron transfer using various aromatic substituted phenylcyclopropanes provided strong evidence that electron transfer occurs. The reaction of cis-2-deutero-1-phenylcyclopropane (PC-d) with NMN established that cycloaddition is stepwise rather than concerted and that both syn and anti reactive intermediates are equally accessible.

  9. Rapid gas hydrate formation process

    SciTech Connect

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  10. Evaporation Rate Study and NDMA Formation from UDMH/NO2 Reaction Products

    NASA Technical Reports Server (NTRS)

    Buchanan, Vanessa D.; Dee, Louis A.; Baker, David L.

    2003-01-01

    Laboratory samples of uns-dimethylhydrazine (UDMH) fuel/oxidizer (nitrogen dioxide) non-combustion reaction products (UFORP) were prepared using a unique permeation tube technology. Also, a synthetic UFORP was prepared from UDMH, N-nitrosodimethylamine (NDMA), dimethylammonium nitrate, sodium nitrite and purified water. The evaporation rate of UFORP and synthetic UFORP was determined under space vacuum (approx 10(exp -3) Torr) at -40 ?C and 0 ?C. The material remaining was analyzed and showed that the UFORP weight and NDMA concentration decreased over time; however, NDMA had not completely evaporated. Over 85% of the weight was removed by subjecting the UFORP to 10(-3) Torr for 7 hours at -40 ?C and 4 hours at 0 ?C. A mixture of dimethylammonium nitrate and sodium nitrite formed NDMA at a rapid rate in a moist air environment. A sample of UFORP residue was analyzed for formation of NDMA under various conditions. It was found that NDMA was not formed unless nitrite was added.

  11. Intramolecular condensation reactions of {alpha},{omega}-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes

    SciTech Connect

    Loy, D.A.; Carpenter, J.P.; Myers, S.A.; Assink, R.A.; Small, J.H.; Greaves, J.; Shea, K.J.

    1996-09-04

    In this paper, we used mass spectrometry and {sup 29}Si NMR spectroscopy to discover that the length of the alkylene-bridging groups had a pronounced effect on the competition between cyclization and polymerization of {alpha},{omega}-bis(triethoxysilyl)alkanes and on the formation of polymeric gels. While the intramolecular reaction clearly slows gelation, the cyclic disilsesquioxanes are still tetrafunctional monomers theoretically capable of forming polymeric gels. If the ring structures, which bear a striking resemblence to carbohydrates, are preserved through the polymerization, the resulting poly(cyclic disilsesquioxane) gels may have structural similarities to branched or cross-linked carbohydrates, such as cellulose or chitosan. Under base-catalyzed sol-gel polymerization conditions, 3 and 4 (six- and seven-membered cyclic disilsesquioxanes, respectively) quickly reacted to give gels with significant ring opening as determined from the {sup 29}Si chemical shifts in solid-state (CP MAS) NMR spectra. However, gels prepared under acidic conditions reveal some or all of the cyclic disilsesquioxane functionality was preserved in the polymers. 13 refs., 1 fig.

  12. Stochastic Modeling of CO2 Migrations and Chemical Reactions in Deep Saline Formations

    NASA Astrophysics Data System (ADS)

    Ni, C.; Lee, I.; Lin, C.

    2013-12-01

    Carbon capture and storage (CCS) has been recognized the feasible technology that can significant reduce the anthropogenic CO2 emissions from large point sources. The CO2 injection in geological formations is one of the options to permanently store the captured CO2. Based on this concept a large number of target formations have been identified and intensively investigated with different types of techniques such as the hydrogeophysical experiments or numerical simulations. The numerical simulations of CO2 migrations in saline formations recently gather much attention because a number of models are available for this purpose and there are potential sites existing in many countries. The lower part of Cholan Formation (CF) near Changhua Coastal Industrial Park (CCIP) in west central Taiwan was identified the largest potential site for CO2 sequestration. The top elevations of the KF in this area varies from 1300 to 1700m below the sea level. Laboratory experiment showed that the permeability of CF is 10-14 to 10-12 m2. Over the years the offshore seismic survey and limited onshore borehole logs have provided information for the simulation of CO2 migration in the CF although the original investigations might not focus on the purpose of CO2 sequestration. In this study we modify the TOUGHREACT model to consider the small-scale heterogeneity in target formation and the cap rock of upper CF. A Monte Carlo Simulation (MCS) approach based on the TOUGHREACT model is employed to quantify the effect of small-scale heterogeneity on the CO2 migrations and hydrochemical reactions in the CF. We assume that the small-scale variability of permeability in KF can be described with a known Gaussian distribution. Therefore, the Gaussian type random field generator such as Sequential Gaussian Simulation (SGSIM) in Geostatistical Software Library (GSLIB) can be used to provide the random permeability realizations for the MCS. A variety of statistical parameters such as the variances and

  13. Formations of Bacteria-like Textures by dynamic reactions in Meteorite and Syntheses

    NASA Astrophysics Data System (ADS)

    Miura, Y.

    2009-05-01

    fixings on iron plates at author's laboratory [4]. 5. Summary 1) Spherule- chained texture with Fe, Ni and Cl has been obtained at the fusion crust of the Kuga iron meteorite found in Japan. 2) As the Kuga iron meteorite is different with the Martian meteorite ALH84001 with composition and formation steps, bacteria-like texture of the Kuga meteorite is first significant example to form fossil-like texture by dynamic reaction of materials in the Solar System. Acknowledgements Author thanks to Dr. T. Kato, Yamaguchi University, for interpretation on bacteria-like texture. References: [1] Miura Y.(2008) 5th AOGS (Asia- Oceania Geosciences Society) Annual Meet. (Busan, Korea), CD#PS07- ST31-A22. [2] Miura Y.(2008). Meteoritics & Planetary Science (USA), 43-7, #5203. [3] McKay D.S. et al. (1996): Science, 273, 924-930. [4]Miura Y. (2009): 6th AGOS (submitted )

  14. THE GAS PHASE REACTION OF OZONE WITH 1,3-BUTADIENE: FORMATION YIELDS OF SOME TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separa...

  15. Synthesis of Multiring Fused 2-Pyridones via a Nitrene Insertion Reaction: Fluorescent Modulators of α-Synuclein Amyloid Formation.

    PubMed

    Singh, Pardeep; Chorell, Erik; Krishnan, K Syam; Kindahl, Tomas; Åden, Jörgen; Wittung-Stafshede, Pernilla; Almqvist, Fredrik

    2015-12-18

    An efficient, straightforward method for the synthesis of thiazolo-2-pyridone embedded peptidomimetic polyheterocycles via a catalyst-free, microwave-assisted, intramolecular C-H amination reaction is reported. All the synthesized polyheterocycles were evaluated for their fluorescent properties and effect on α-synuclein amyloid formation. PMID:26650849

  16. Evaluation of existence region and formation time of particle accumulation structure (PAS) in half-zone liquid bridge

    NASA Astrophysics Data System (ADS)

    Gotoda, M.; Sano, T.; Kaneko, T.; Ueno, I.

    2015-03-01

    We focused on the particle accumulation structure (PAS) produced by the thermocapillary effect in a half-zone liquid bridge. Although models of the formation of the PAS have been previously proposed, they have not been experimentally verified. An assessment of the region in which the PAS exists is very subjective and often dependent on the observer, and this has necessitated the development of an objective and quantitative evaluation method. We therefore conducted a series of experiments to verify the physical model of the particle path lines in a rotating frame of reference using the fundamental frequency of the hydrothermal wave. We evaluated the intensity of the particle accumulation based on a modification of the "accumulation measure" proposed by Kuhlmann and Muldoon (Phys. Rev. E, 2012) to objectively and quantitatively determine the existence region of the SL-1 PAS. The results of the quantitative experiment revealed that the best aspect ratio (ratio of the height to radius) of the liquid bridge for the SL-1 PAS was about 0.64, and that the PAS formation time was nearly the same as the thermal diffusion time under the considered conditions (184 words, within 200 words).

  17. Formation of Po isotopes in the reactions {sup 27}Al + {sup 175}Lu and {sup 31}P + {sup 169}Tm

    SciTech Connect

    Andreev, A.N.; Bogdanov, D.D.; Eremin, A.V.

    1995-05-01

    The excitation functions and the cross sections for the formation of {sup 192-198}Po isotopes in the reactions {sup 27}Al + {sup 175}Lu and {sup 31}P + {sup 169}Tm are measured. A comparison of the results obtained for these reactions with the data on the cross sections for the formation of Po isotopes in the reaction {sup 100}Mo + {sup 92-100}Mo leads to the conclusion that the characteristics of the evaporation channel do not depend on the mass of the bombarding ion up to the complete symmetry in the input channel. It is shown that the experimental data can be adequately described using the statistical approach to the deexcitation of a compound nucleus only under the assumption that the liquid-drop fission barrier is reduced significantly for neutron-deficient Po isotopes. 21 refs., 5 figs., 2 tabs.

  18. Formate-derived H2 , a driver of hydrogenotrophic processes in the root-zone of a methane-emitting fen.

    PubMed

    Hunger, Sindy; Schmidt, Oliver; Gößner, Anita S; Drake, Harold L

    2016-09-01

    Wetlands are important sources of globally emitted methane. Plants mediate much of that emission by releasing root-derived organic carbon, including formate, a direct precursor of methane. Thus, the objective of this study was to resolve formate-driven processes potentially linked to methanogenesis in the fen root-zone. Although, formate was anticipated to directly trigger methanogenesis, the rapid anaerobic consumption of formate by Carex roots unexpectedly yielded H2 and CO2 via enzymes such as formate-H2 -lyase (FHL), and likewise appeared to enhance the utilization of organic carbon. Collectively, 57 [FeFe]- and [NiFe]-hydrogenase-containing family level phylotypes potentially linked to FHL activity were detected. Under anoxic conditions, root-derived fermentative Citrobacter and Hafnia isolates produced H2 from formate via FHL. Formate-derived H2 fueled methanogenesis and acetogenesis, and methanogenic (Methanoregula, Methanobacterium, Methanocella) and acetogenic (Acetonema, Clostridum, Sporomusa) genera potentially linked to these hydrogenotrophic activities were identified. The findings (i) provide novel insights on highly diverse root-associated FHL-containing taxa that can augment secondary hydrogenotrophic processes via the production of formate-derived H2 , (ii) demonstrate that formate can have a 'priming' effect on the utilization of organic carbon, and (iii) raise questions regarding the fate of formate-derived H2 when it diffuses away from the root-zone. PMID:26999575

  19. Elucidation of reaction mechanism involved in the formation of LaNiO3 from XRD and TG analysis

    NASA Astrophysics Data System (ADS)

    Dharmadhikari, Dipti V.; Athawale, Anjali A.

    2013-06-01

    The present work is focused on the synthesis and elucidation of reaction mechanism involved in the formation of LaNiO3 with the help of X-ray diffraction (XRD) and thermogravimetric (TG) analysis. LaNiO3 was synthesized by hydrothermal method by heating at 160°C under autogenous pressure for 6h. Pure phase product was obtained after calcining the hydrothermally activated product for 6h at 700°C. The various phases of the product obtained after hydrothermal treatment and calcination followed by the formation of pure phase nanocrystalline lanthanum nickel oxide could be determined from XRD analysis of the samples. The reaction mechanism and phase formation temperature has been interpreted by thermogravimetric analysis of the hydrothermally synthesized product and XRD analysis.

  20. The formation of komatiites by melt accumulation and segregation in the transition zone

    NASA Astrophysics Data System (ADS)

    Arndt, Nicholas T.; Schmeling, Harro; Kohl, Svenja

    2014-05-01

    Komatiites are highly magnesian volcanic rocks characteristic of the Archean. There are three types: Al-depleted komatiites, which have low Al/Ti, relatively high concentrations of incompatible elements and depleted HREE; Al-undepleted komatiites, with chondritic Al/Ti and slightly depleted LREE; and Al-enriched komatiites, with high Al/Ti, low concentrations of incompatible elements and extremely depleted LREE. Petrological and geochemical information indicates that these rocks formed by melting in hot mantle plumes at pressures greater than about 13GPa. In a model developed by Robin-Popieul et al (2010 J Petrol 53: 2191), Al-depleted komatiites form by batch melting and segregate at 13GPa leaving a garnet-rich residue while Al-enriched komatiites form by advanced fractional melting at shallower depth. Two aspects of the model posed problems. First, at the depths where the Al-depleted komatiite is generated, the melt is denser than mantle olivine, and it is unclear how this melt separated from its source. Second, the compositions of melts produced by fractional melting are extremely variable, depending delicately on the degree of partial melting, yet the compositions of packages of erupted Al-enriched komatiites are relatively uniform. A solution to these problems is provided by the investigation of the physics of melting and melt segregation within hot upwelling mantle described in the companion abstract by Schmeling et al. These studies showed that when the level of neutral buoyancy lies above the depth of onset of melting, the dense melt accumulates behind the solid phases within the rising plume, only to escape as high-degree melt once the plume rises above the neutral buoyancy level. This pattern of melting explains the formation of Al-depleted komatiites. Under other conditions, the melt accumulates within the plume as a series of standing waves that escape upwards as they reach the level of neutral buoyancy. This process progressively depletes the source in

  1. Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber

    NASA Astrophysics Data System (ADS)

    Platt, S. M.; El Haddad, I.; Zardini, A. A.; Clairotte, M.; Astorga, C.; Wolf, R.; Slowik, J. G.; Temime-Roussel, B.; Marchand, N.; Ježek, I.; Drinovec, L.; Močnik, G.; Möhler, O.; Richter, R.; Barmet, P.; Bianchi, F.; Baltensperger, U.; Prévôt, A. S. H.

    2012-10-01

    We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of aerosols from different emissions sources without limitation from the instruments or facilities available at any single site. The chamber can be mounted on a trailer for transport to host facilities or for mobile measurements. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric photochemistry can be accurately simulated over a range of temperatures from -7-25 °C. A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 molecules cm-3 s-1 was determined at 25 °C. Further, we present the first application of the mobile chamber and demonstrate its utility by quantifying primary organic aerosol (POA) emission and secondary organic aerosol (SOA) production from a Euro 5 light duty gasoline vehicle. Exhaust emissions were sampled during the New European Driving Cycle (NEDC), the standard driving cycle for European regulatory purposes, and injected into the chamber. The relative concentrations of oxides of nitrogen (NOx) and total hydrocarbon (THC) during the aging of emissions inside the chamber were controlled using an injection system developed as a part of the new mobile chamber set up. Total OA (POA + SOA) emission factors of (370 ± 18) × 10-3 g kg-1 fuel, or (14.6 ± 0.8) × 10-3 g km-1, after aging, were calculated from concentrations measured inside the smog chamber during two experiments. The average SOA/POA ratio for the two experiments was 15.1, a much larger increase than has previously been seen for diesel vehicles, where smog chamber studies have found SOA/POA ratios of 1.3-1.7. Due to this SOA formation, carbonaceous particulate matter (PM) emissions from a gasoline vehicle may approach those of a diesel vehicle of the same class. Furthermore, with the advent of emission controls requiring the use of diesel particle filters, gasoline vehicle emissions

  2. Ozone consumption and volatile byproduct formation from surface reactions with aircraft cabin materials and clothing fabrics

    NASA Astrophysics Data System (ADS)

    Coleman, Beverly K.; Destaillats, Hugo; Hodgson, Alfred T.; Nazaroff, William W.

    We measured ozone consumption and byproduct formation on materials commonly found in aircraft cabins at flight-relevant conditions. Two series of small-chamber experiments were conducted, with most runs at low relative humidity (10%) and high air-exchange rate (˜20 h -1). New and used cabin materials (seat fabric, carpet, and plastic) and laundered and worn clothing fabrics (cotton, polyester, and wool) were studied. We measured ozone deposition to many material samples, and we measured ozone uptake and primary and secondary emissions of volatile organic compounds (VOCs) from a subset of samples. Deposition velocities ranged from 0.06 to 0.54 cm s -1. Emissions of VOCs were higher with ozone than without ozone in every case. The most commonly detected secondary emissions were C 1 through C 10 saturated aldehydes and the squalene oxidation products 6-methyl-5-hepten-2-one and acetone. For the compounds measured, summed VOC emission rates in the presence of 55-128 ppb (residual level) ozone ranged from 1.0 to 8.9 μmol h -1 m -2. Total byproduct yield ranged from 0.07 to 0.24 moles of product volatilized per mole of ozone consumed. Results were used to estimate the relative contribution of different materials to ozone deposition and byproduct emissions in a typical aircraft cabin. The dominant contributor to both was clothing fabrics, followed by seat fabric. Results indicate that ozone reactions with surfaces substantially reduce the ozone concentration in the cabin but also generate volatile byproducts of potential concern for the health and comfort of passengers and crew.

  3. Reaction kinetics and oxidation product formation in the degradation of acetaminophen by ferrate (VI).

    PubMed

    Wang, Hongyu; Liu, Yibing; Jiang, Jia-Qian

    2016-07-01

    This paper investigates the degradation of acetaminophen (AAP) in aqueous solutions by ferrate (VI), aiming to propose the kinetics, pathways and the oxidation products' formation in the AAP degradation. A series of jar tests were undertaken over ferrate (VI) dosages (molar ratios of ferrate (VI):AAP, 5:1 to 25:1) and pH values (4-11). The effects of co-existing ions (0.2-5 mM) and humic acid (10-50 mg l(-1)) on the AAP removal were investigated. Ferrate (VI) can remove 99.6% AAP (from 1000 μg l(-1)) in 60 min under study conditions when majority of the AAP reduction occurred in the first 5 min. The treatment performance depended on the ferrate(VI) dosage, pH and the type and strength of co-existing ions and humic acid. Raising ferrate (VI) dosage with optimal pH 7 improved the AAP degradation. In the presence of humic acid, the AAP degradation by ferrate (VI) was promoted in a short period (<30 min) but then inhibited with increasing in humic acid contents. The presence of Al(3+), CO3(2-) and PO4(3-) ions declined but the existence of K(+), Na(+), Mg(2+) and Ca(2+) ions can improve the AAP removal. The catalytic function of Al(3+) on the decomposition of ferrate (VI) in aqueous solution was found. The kinetics of the reaction between ferrate (VI) and AAP was pseudo first-order for ferrete (VI) and pseudo second-order for AAP. The pseudo rate constant of ferrate (VI) with AAP was 1.4 × 10(-5) L(2) mg(-2) min(-1). Three oxidation products (OPs) were identified and the AAP degradation pathways were proposed. PMID:27155474

  4. A complex cortical reaction leads to formation of the fertilization envelope in the lobster, Homarus.

    PubMed

    Talbot, P; Goudeau, M

    1988-01-01

    We have examined the formation of the fertilization envelope in the lobsters Homarus americanus and H gammarus. Oocytes were fixed for electron microscopy either in the ovary or following extrusion from the gonopore. Mature ovarian oocytes are surrounded by a coat (envelope 1), which is comprised of small electron-dense granules and structures resembling "bottlebrushes." At least part of this coat is synthesized by the follicle cells of the ovary. The cortex of ovarian oocytes contains four types of vesicles that we refer to as high-density vesicles (HDV), low-density vesicles (LDV), moderately dense vesicles (MDV), and ring vesicles (RV). Oocytes that were electrically extruded from the gonopore and fixed immediately had an envelope identical to that of ovarian oocytes. The cortex of gonopore oocytes contained the four types of vesicles found in ovarian oocytes. When unfertilized gonopore oocytes were allowed to incubate in sea water, the oocyte cortex appeared unaltered, but envelope 1 swelled and the bottlebrushes dispersed. When recently fertilized oocytes were fixed during natural spawning or following in-vitro fertilization, each type of vesicle was released in sequence from the cortex of the oocyte. The contents of the HDV and LDV appeared first in the perivitelline space, but their fate could not be determined at later times. The ring-shaped elements of the RV and the moderately electron-dense material of the MDV were released exocytotically somewhat later; these materials coalesced in the perivitelline space to form a new coat (envelope 2). Envelope 1 subsequently condensed to its original thickness and appeared firmly attached to envelope 2. Our results show that the fertilized lobster egg is surrounded by two discrete coats. The outer coat, which is formed in the ovary, undergoes a swelling/condensation cycle at spawning. The inner coat originates from a complex cortical reaction. Together these coats comprise the fertilization envelope of the lobster

  5. The C(3P) + NH3 Reaction in Interstellar Chemistry. I. Investigation of the Product Formation Channels

    NASA Astrophysics Data System (ADS)

    Bourgalais, Jérémy; Capron, Michael; Abhinavam Kailasanathan, Ranjith Kumar; Osborn, David L.; Hickson, Kevin M.; Loison, Jean-Christophe; Wakelam, Valentine; Goulay, Fabien; Le Picard, Sébastien D.

    2015-10-01

    The product formation channels of ground state carbon atoms, C(3P), reacting with ammonia, NH3, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH3 reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H2CN production channel represents 100% of the product yield for this reaction. Kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.

  6. Relevance of the H2 + O reaction pathway for the surface formation of interstellar water. Combined experimental and modeling study

    NASA Astrophysics Data System (ADS)

    Lamberts, T.; Cuppen, H. M.; Fedoseev, G.; Ioppolo, S.; Chuang, K.-J.; Linnartz, H.

    2014-10-01

    The formation of interstellar water is commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas-phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature-programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants were brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The water detected with the quadrupole mass spectrometer upon TPD was found to originate mainly from contamination in the chamber itself. However, if water is produced in small quantities on the surface through H2 + O, this can only be explained by a combined classical and tunneled reaction mechanism. An absolutely conservative upper limit for the reaction rate was derived with a microscopic kinetic Monte Carlo model that converts the upper limit into the highest possible reaction rate. Incorporating this rate into simulation runs for astrochemically relevant parameters shows that the upper limit to the contribution of the reaction H2 + O in OH, and hence water formation, is 11% in dense interstellar clouds. Our combined experimental and theoretical results indicate, however, that this contribution is most likely much lower.

  7. Formation of slow molecules in chemical reactions in crossed molecular beams

    NASA Astrophysics Data System (ADS)

    Tscherbul, T. V.; Barinovs, Ğ.; Kłos, J.; Krems, R. V.

    2008-08-01

    We demonstrate that chemical reactions in collisions of molecular beams can generally produce low-velocity molecules in the laboratory-fixed frame. Our analysis shows that collisions of beams may simultaneously yield slow reactant molecules and slow products. The reaction products are formed in selected rovibrational states and scattered in a specific direction, which can be controlled by tuning the kinetic energies of the incident beams and the angle between the beams. Our calculations indicate that chemical reactions of polar alkali-metal dimers are barrierless and we suggest that chemical reactions involving alkali-metal dimers may be particularly suitable for producing slow molecules in crossed beams.

  8. Integrating crystallographic data and phase equilibria to quantify P-T-X evolution during reaction texture formation

    NASA Astrophysics Data System (ADS)

    Goergen, E. T.

    2008-12-01

    Coronal symplectitic reaction textures occur as a result of changes in intensive variables. This variation can arise as a result of changes in pressure and/or temperature or result from modification of bulk composition due to an influx of fluids. These processes lead to development of chemical potential gradients that drive diffusion and are responsible for the vermicular nature of symplectitic reaction textures. Deducing the P-T conditions of reaction and the P-T-X path responsible for texture formation is a difficult but critical step in interpreting the crystallization history of symplectites as well as providing appropriate boundary conditions for modeling texture development. Symplectite textures in gedrite-cordierite rocks from Thor-Odin gneiss dome in British Columbia, Canada preserve spl+crd, an+crd, and crn+crd two-phase assemblages after sillimanite porphyroblasts. These two-phase assemblages are not present as a consistent progression of layers as in other examples of symplectitic textures, but occur in a variety of locations with respect to the central sillimanite porphyroblast that are also unrelated to adjacent matrix mineral assemblages. This suggests that the chemical potential gradients responsible for symplectite formation are not consistent around the texture. The two-phase symplectitic assemblages are encased by a rim of polygonal cordierite. These inconsistent relationships make proper interpretation of the relative timing of symplectite and cordierite rim growth, as well as establishing the P-T-X conditions and kinetics of reaction difficult using traditional methods. The integration of mineral chemistry, phase-equilibria, crystallographic analysis and image analysis has provided a method of determining the P-T conditions at which symplectite formation began as well as providing information on how the size and nature of the chemical system evolved during reaction and growth. EBSD data from cordierite rims and the sillimanite porphyroblasts

  9. 2D Model for Diffusion of Oxygen with Biochemical Reaction During Biofilm Formation Process in Static Aqueous Medium

    NASA Astrophysics Data System (ADS)

    Puyate, Y. T.; Rim-Rukeh, A.

    A 2D model that describes diffusion of oxygen with biochemical reaction during biofilm formation process in static aqueous medium is presented. The analysis is based on X60 steel placed at the bottom of a container containing produced water inoculated with Leptothrix discophora (iron-oxidizing bacteria). These bacteria form biofilms on the exposed surfaces of the metal. The biofilm-microorganisms absorb oxygen from the produced water through biochemical reaction, resulting in transfer of oxygen from the bulk liquid phase to the biofilm. Predictions of the model are compared with experimental data and good agreement is obtained.

  10. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    PubMed

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation. PMID:27485276

  11. Coke formation in a zeolite crystal during the methanol-to-hydrocarbons reaction as studied with atom probe tomography

    DOE PAGESBeta

    Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D. A. Matthijs; Meirer, Florian; Bare, Simon R.; Weckhuysen, Bert M.

    2016-08-03

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using 13C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid sitemore » density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. Here, this nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.« less

  12. Dentin bonding performance using Weibull statistics and evaluation of acid-base resistant zone formation of recently introduced adhesives.

    PubMed

    Guan, Rui; Takagaki, Tomohiro; Matsui, Naoko; Sato, Takaaki; Burrow, Michael F; Palamara, Joseph; Nikaido, Toru; Tagami, Junji

    2016-07-30

    Dentin bonding durability of recently introduced dental adhesives: Clearfil SE Bond 2 (SE2), Optibond XTR (XTR), and Scotchbond Universal (SBU) was investigated using Weibull analysis as well as analysis of the micromorphological features of the acid-base resistant zone (ABRZ) created for the adhesives. The bonding procedures of SBU were divided into three subgroups: self-etch (SBS), phosphoric acid (PA) etching on moist (SBM) or dry dentin (SBD). All groups were thermocycled for 0, 5,000 and 10,000 cycles followed by microtensile bond strength testing. Acid-base challenge was undertaken before SEM and TEM observations of the adhesive interface. The etch-and-rinse method with SBU (SBM and SBD) created inferior interfaces on the dentin surface which resulted in reduced bond durability. ABRZ formation was detected with the self-etch adhesive systems; SE2, XTR and SBS. In the PA etching protocols of SBM and SBD, a thick hybrid layer but no ABRZ was detected, which might affect dentin bond durability. PMID:27335136

  13. DOE capabilities for in-situ characterization and monitoring of formation properties in the vadose zone. Revision 2

    SciTech Connect

    Hearst, J.R.; Brodeur, J.R.; Koizumi, C.J.; Conaway, J.G.; Mikesell, J.L.; Nelson, P.H.; Stromswold, D.C.; Wilson, R.D.

    1993-09-01

    The DOE Environmental Restoration (ER) Program faces the difficult task of characterizing the properties of the subsurface and identifying and mapping a large number of contaminants at landfills, surface disposal areas, spill sites, nuclear waste tanks, and subsurface contaminant plumes throughout the complex of DOE facilities. Geophysical borehole logs can measure formation properties such as bulk density, water content, and lithology, and can quantitatively analyze for radionuclides and such elements as chlorine and heavy metals. Since these measurements can be repeated as desired, they can be used for both initial characterization and monitoring of changes in contaminant concentration and water content (sometimes linked to contaminant migration), at a fraction of the cost of conventional sampling. The techniques developed at several DOE laboratories, and the experience that we have gained in making in-situ measurements in the vadose zone, are applicable to problems at many other DOE sites. Moreover, they can capitalize on existing inventories of boreholes. By building on this experience workers involved in ER projects at those sites should be able to obtain high-quality data at substantial reductions in cost and time.

  14. A high affinity RIM-binding protein/Aplip1 interaction prevents the formation of ectopic axonal active zones

    PubMed Central

    Siebert, Matthias; Böhme, Mathias A; Driller, Jan H; Babikir, Husam; Mampell, Malou M; Rey, Ulises; Ramesh, Niraja; Matkovic, Tanja; Holton, Nicole; Reddy-Alla, Suneel; Göttfert, Fabian; Kamin, Dirk; Quentin, Christine; Klinedinst, Susan; Andlauer, Till FM; Hell, Stefan W; Collins, Catherine A; Wahl, Markus C; Loll, Bernhard; Sigrist, Stephan J

    2015-01-01

    Synaptic vesicles (SVs) fuse at active zones (AZs) covered by a protein scaffold, at Drosophila synapses comprised of ELKS family member Bruchpilot (BRP) and RIM-binding protein (RBP). We here demonstrate axonal co-transport of BRP and RBP using intravital live imaging, with both proteins co-accumulating in axonal aggregates of several transport mutants. RBP, via its C-terminal Src-homology 3 (SH3) domains, binds Aplip1/JIP1, a transport adaptor involved in kinesin-dependent SV transport. We show in atomic detail that RBP C-terminal SH3 domains bind a proline-rich (PxxP) motif of Aplip1/JIP1 with submicromolar affinity. Pointmutating this PxxP motif provoked formation of ectopic AZ-like structures at axonal membranes. Direct interactions between AZ proteins and transport adaptors seem to provide complex avidity and shield synaptic interaction surfaces of pre-assembled scaffold protein transport complexes, thus, favouring physiological synaptic AZ assembly over premature assembly at axonal membranes. DOI: http://dx.doi.org/10.7554/eLife.06935.001 PMID:26274777

  15. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  16. Formation of phenol under conditions of the reaction of oxidative carbonylation of benzene to benzoic acid

    SciTech Connect

    Kalinovsky, I.O.; Leshcheva, A.N.; Pogorelov, V.V.; Gelbshtein, A.I.

    1993-12-31

    This paper describes conditions for the oxidation of benzene to phenol. It is shown that a reaction mixture of water, carbon monoxide, and oxygen are essential to the oxidation. The oxidation is a side reaction found to occur during the oxidative carbonylation of benzene to benzoic acid in a medium of trifluoroacetic acid.

  17. Reactions of nitroso hetero-Diels-Alder cycloadducts with azides: stereoselective formation of triazolines and aziridines.

    PubMed

    Bodnar, Brian S; Miller, Marvin J

    2007-05-11

    The addition of azides to acylnitroso hetero-Diels-Alder cycloadducts derived from cyclopentadiene affords exo-triazolines in excellent yield. The reaction is greatly affected by the level of alkene strain, while sterically demanding azides do not hinder the reaction. Conversion of the triazolines to aziridines is also described. PMID:17429998

  18. Reactions of Nitroso Hetero Diels-Alder Cycloadducts with Azides: Stereoselective Formation of Triazolines and Aziridines

    PubMed Central

    Bodnar, Brian S.

    2011-01-01

    The addition of azides to acylnitroso hetero Diels-Alder cycloadducts derived from cyclopentadiene affords exo triazolines in excellent yield. The reaction is greatly affected by reducing the level of alkene strain, while sterically demanding azides do not hinder the reaction. Conversion of the triazolines to aziridines is also described. PMID:17429998

  19. Styrene oxide DNA adducts: in vitro reaction and sensitive detection of modified oligonucleotides using capillary zone electrophoresis interfaced to electrospray mass spectrometry.

    PubMed

    Schrader, W; Linscheid, M

    1997-01-01

    Styrene is one of the most important synthetic chemicals in the world and is subject to investigations concerning carcinogenicity and mutagenicity due to the active metabolite, styrene-7,8-oxide. This epoxide shows a tendency to react, among others, with DNA and DNA constituents. The in vitro reaction of styrene oxide with DNA was investigated by cleaving incubated calf thymus DNA with two different enzymes, namely Benzonase and alkaline phosphatase, to obtain oligonucleotides of the type n-nucleotide-(n-1)-phosphate with chain length from 2 to 8 bases. Alkylated and nonalkylated nucleotides were separated in groups according to their chain length using capillary zone electrophoresis and were detected with electrospray mass spectrometry. This improvement in sensitivity made it possible to obtain new information about the reaction of styrene oxide with DNA, especially to detect unknown reaction products. The results indicate that primarily purine bases were alkylated by styrene oxide before pyrimidine bases, which react with higher concentrations of styrene oxide. This means that in addition to the already reported adducts in DNA at the N-7-, O6- and N2-position of guanine also adducts at the nucleophilic sites of adenine can be found using mass spectrometry. We anticipate for the future this procedure will allow us to investigate base sequence specific reactions as well as interactions from xenobiotics and cytostatic drugs, since reaction products would directly be detectable. PMID:9285042

  20. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    NASA Astrophysics Data System (ADS)

    Ehn, M.; Kleist, E.; Junninen, H.; Petäjä, T.; Lönn, G.; Schobesberger, S.; Dal Maso, M.; Trimborn, A.; Kulmala, M.; Worsnop, D. R.; Wahner, A.; Wildt, J.; Mentel, Th. F.

    2012-06-01

    High molecular weight (300-650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3-) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7-1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4- (Hyytiälä) and C3F5O2- (JPAC). The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4-5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1-1 ppt (~106-107 molec cm-3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and

  1. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    NASA Astrophysics Data System (ADS)

    Ehn, M.; Kleist, E.; Junninen, H.; Petäjä, T.; Lönn, G.; Schobesberger, S.; Dal Maso, M.; Trimborn, A.; Kulmala, M.; Worsnop, D. R.; Wahner, A.; Wildt, J.; Mentel, Th. F.

    2012-02-01

    High molecular weight (300-650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night during spring and summer in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3-) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7-1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4- (Hyytiälä) and C3F5O2- (JPAC). The most abundant products in the ion spectra were identified as C105H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4-5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1-1 ppt (~106-107 molec cm-3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and

  2. Opaque Mineral Assemblages at Chondrule Boundaries in the Vigarano CV Chondrite: Evidence for Gas-Solid Reactions Following Chondrule Formation

    NASA Technical Reports Server (NTRS)

    Lauretta, Dante S.

    2004-01-01

    Recent studies of opaque minerals in primitive ordinary chondrites suggest that metal grains exposed at chondrule boundaries were corroded when volatile elements recondensed after the transient heating event responsible for chondrule formation. Metal grains at chondrule boundaries in the Bishunpur (LL3.1) chondrite are rimmed by troilite and fayalite. If these layers formed by gas solid reaction, then the composition of the corrosion products can provide information on the chondrule formation environment. Given the broad similarities among chondrules from different chondrite groups, similar scale layers should occur on chondrules in other primitive meteorite groups. Here I report on metal grains at chondrule boundaries in Vigarano (CV3).

  3. Lower molecular weight hydrocarbon formation in an open flow system by Fischer Tropsch reaction. [in primitive solar system

    NASA Technical Reports Server (NTRS)

    Hobo, T.; Ponnamperuma, C.; Hook, A. G.; Donn, B.

    1978-01-01

    A Fischer Tropsch type mechanism has been proposed for the synthesis of organic compounds in the primitive solar system. The evidence for hydrocarbon formation, especially those of higher molecular weight, under simulated conditions of the early solar nebula has been presented (Studier et al., 1968, 1972; Gelpi et al., 1970). In this paper, we report studies on the formation of specifically the lower molecular weight hydrocarbons. By using an open flow reaction system and two closed systems, several factors which may affect the production of these compounds have been examined.

  4. The Formation Of Glycerol Monodecanoate By A Dehydration Condensation Reaction: Increasing The Chemical Complexity Of Amphiphiles On The Early Earth

    NASA Astrophysics Data System (ADS)

    Apel, Charles L.; Deamer, David W.

    2005-08-01

    Dehydration/condensation reactions between organic molecules in the prebiotic environment increased the inventory and complexity of organic compounds available for self-assembly into primitive cellular organisms. As a model of such reactions and to demonstrate this principle, we have investigated the esterification reaction between glycerol and decanoic acid that forms glycerol monodecanoate (GMD). This amphiphile enhances robustness of self-assembled membranous structures of carboxylic acids to the potentially disruptive effects of pH, divalent cation binding and osmotic stress. Experimental variables included temperature, water activity and hydrolysis of the resulting ester product, providing insights into the environmental conditions that would favor the formation and stability of this more evolved amphiphile. At temperatures exceeding 50 ∘C, the ester product formed even in the presence of bulk water, suggesting that the reaction occurs at the liquid interface of the two reactants and that the products segregate in the two immiscible layers, thereby reducing hydrolytic back reactions. This implies that esterification reactions were likely to be common in the prebiotic environment as reactants underwent cycles of wetting and drying on rare early landmasses at elevated temperatures

  5. Ab initio reaction kinetics of hydrogen abstraction from methyl formate by hydrogen, methyl, oxygen, hydroxyl, and hydroperoxy radicals.

    PubMed

    Tan, Ting; Pavone, Michele; Krisiloff, David B; Carter, Emily A

    2012-08-23

    Combustion of renewable biofuels, including energy-dense biodiesel, is expected to contribute significantly toward meeting future energy demands in the transportation sector. Elucidating detailed reaction mechanisms will be crucial to understanding biodiesel combustion, and hydrogen abstraction reactions are expected to dominate biodiesel combustion during ignition. In this work, we investigate hydrogen abstraction by the radicals H·, CH(3)·, O·, HO(2)·, and OH· from methyl formate, the simplest surrogate for complex biodiesels. We evaluate the H abstraction barrier heights and reaction enthalpies, using multireference correlated wave function methods including size-extensivity corrections and extrapolation to the complete basis set limit. The barrier heights predicted for abstraction by H·, CH(3)·, and O· are in excellent agreement with derived experimental values, with errors ≤1 kcal/mol. We also predict the reaction energetics for forming reactant complexes, transition states, and product complexes for reactions involving HO(2)· and OH·. High-pressure-limit rate constants are computed using transition state theory within the separable-hindered-rotor approximation for torsions and the harmonic oscillator approximation for other vibrational modes. The predicted rate constants differ significantly from those appearing in the latest combustion kinetics models of these reactions. PMID:22830521

  6. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    SciTech Connect

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-10

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  7. RAPID ASSOCIATION REACTIONS AT LOW PRESSURE: IMPACT ON THE FORMATION OF HYDROCARBONS ON TITAN

    SciTech Connect

    Vuitton, V.; Klippenstein, S. J. E-mail: yelle@lpl.arizona.edu E-mail: sjk@anl.gov

    2012-01-01

    Photochemical models of Titan's atmosphere predict that three-body association reactions are the main production route for several major hydrocarbons. The kinetic rate constants of these reactions strongly depend on density and are therefore only important in Titan's lower atmosphere. However, radiative association reactions do not depend on pressure. The possible existence of large rates at low density suggests that association reactions could significantly affect the chemistry of Titan's upper atmosphere and better constraints for them are required. The kinetic parameters of these reactions are extremely difficult to constrain by experimental measurements as the low pressure of Titan's upper atmosphere cannot be reproduced in the laboratory. However, in the recent years, theoretical calculations of kinetics parameters have become more and more reliable. We therefore calculated several radical-radical and radical-molecule association reaction rates using transition state theory. The calculations indicate that association reactions are fast even at low pressure for adducts having as few as four C atoms. These drastic changes have however only moderate consequences for Titan's composition. Locally, mole fractions can vary by as much as one order of magnitude but the column-integrated production and condensation rates of hydrocarbons change only by a factor of a few. We discuss the impact of these results for the organic chemistry. It would be very interesting to check the impact of these new rate constants on other environments, such as giant and extrasolar planets as well as the interstellar medium.

  8. Models for hydrogen gasification of coal - Analysis and significance of methane formation reactions

    NASA Astrophysics Data System (ADS)

    Huettinger, K. J.; Kirrmann, H.

    1980-06-01

    A study is reported in which four samples of open-burning coal, one coking type of coal, one-short-flaming (smokeless) coal, as well as defined pvc-pyrolysis residues were gasified in a fixed bed reactor. Three areas of methane formation are analyzed and the results of these methane formations examined. It is found that the methane formation between 500 and 600 C can be traced back to the rupture of methyl groups and methylene bridges. Further, the methane formation between 700 and 800 C is based on the maximum disorder of the paracrystalline coke residue. Finally, the catalytic activity of iron on coke gasification is considered, noting that it leads to the formation of methane above 850 C, and that since iron acts as a catalyst only under pressure, methane formation in this range is noticed only in pressure gasification.

  9. Formation spectra of light kaonic nuclei by in-flight (K¯,N) reactions with a chiral unitary amplitude

    NASA Astrophysics Data System (ADS)

    Yamagata-Sekihara, J.; Jido, D.; Nagahiro, H.; Hirenzaki, S.

    2009-10-01

    We study theoretically the in-flight (K-,N) reactions for the formation of light kaonic nuclear systems to get deeper physical insights on the spectra and to investigate the formation spectra of the reaction that will be observed at new facilities like the Japan Proton Accelerator Research Complex (J-PARC). We show the expected spectra for the formation of the K-pp, K-pn, K-nn, and K--B11 systems that are accessible by the (K-,N) experiments. By considering the conversion part of the Green’s function, we show the missing mass spectra of the (K-,N) reactions in coincident with the particle emissions due to K¯ absorption. To calculate the cross sections, we use the so-called Tρ approximation to evaluate the optical potential. As for the amplitude T, we adopt the chiral unitary amplitude of K¯N channel in vacuum for simplicity. The effects of the p-wave optical potential of Σ(1385) channel and the contributions from K¯0 mixing in He3(K-,n) reaction are also evaluated numerically. We also study the behavior of the poles of kaon Green’s function in nuclear matter. We conclude that He3(K-,n) and He3(K-,p) reaction spectra in coincident with the πΣ emission may show the structure in the kaon bound region indicating the existence of the unstable kaonic nuclear states. As for the C12(K-,p) spectra with the πΣ emission, we may also observe the structure in the bound region, however, we need to evaluate the medium effects carefully for larger nuclei.

  10. Reaction mechanisms in aromatic hydrocarbon formation involving the C{sub 5}H{sub 5} cyclopentadienyl moiety

    SciTech Connect

    Melius, C.F.; Colvin, M.E.; Marinov, N.M.; Pitz, W.J.; Senkan, S.M.

    1996-02-01

    The quantum chemical BAC-MP4 and BAC-MP2 methods have been used to investigate the reaction mechanisms leading to polycyclic aromatic hydrocarbon (PAH) ring formation. In particular the authors have determined the elementary reaction steps in the conversion of two cyclopentadienyl radicals to naphthalene. This reaction mechanism is shown to be an extension of the mechanism occurring in the H atom-assisted conversion of fulvene to benzene. The net reaction involves the formation of dihydrofulvalene, which eliminates a hydrogen atom and then rearranges to form naphthalene through a series of ring closures and openings. The importance of forming the {single_bond}CR({center_dot}){single_bond}CHR{single_bond}CR{prime}{double_bond}CR{double_prime}-moiety, which can undergo rearrangement to form three-carbon-atom ring structures, is illustrated with the C{sub 4}H{sub 7} system. The ability of hydrogen atoms to migrate around the cyclopentadienyl moiety is illustrated both for methyl-cyclopentadiene, C{sub 5}H{sub 5}CH{sub 3}, and dihydrofulvalene, C{sub 5}H{sub 5}C{sub 5}H{sub 5}, as well as for their radical species, C{sub 6}H{sub 7} and C{sub 5}H{sub 5}C{sub 5}H{sub 4}. The mobility of hydrogen in the cyclopentadienyl moiety plays an important role both in providing resonance-stabilized radical products and in creating the {single_bond}CR({center_dot}){single_bond}CHR{single_bond}CR{prime}{double_bond}CR{double_prime}-moiety for ring formation. The results illustrate the radical pathway for converting five-membered rings to aromatic six-membered rings. Furthermore, the results indicate the important catalytic role of H atoms in the aromatic ring formation process.

  11. Formation of medical radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu in photonuclear reactions

    NASA Astrophysics Data System (ADS)

    Danagulyan, A. S.; Hovhannisyan, G. H.; Bakhshiyan, T. M.; Avagyan, R. H.; Avetisyan, A. E.; Kerobyan, I. A.; Dallakyan, R. K.

    2015-06-01

    The possibility of the photonuclear production of radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu is discussed. Reaction yields were measured by the gamma-activation method. The enriched tin isotopes 112, 118Sn and Te and HfO2 of natural isotopic composition were used as targets. The targets were irradiated at the linear electron accelerator of Alikhanian National Science Laboratory (Yerevan) at the energy of 40 MeV. The experimental results obtained in this way reveal that the yield and purity of radioisotopes 111In and 117 mSn are acceptable for their production via photonuclear reactions. Reactions proceeding on targets from Te and HfO2 of natural isotopic composition and leading to the formation of 124Sb and 177Lu have small yields and are hardly appropriate for the photoproduction of these radioisotopes even in the case of enriched targets.

  12. Electromagnetic containerless reaction of samarium with cobalt for the formation of samarium-cobalt alloys

    NASA Technical Reports Server (NTRS)

    Chang, C. W.; Das, D. K.; Kumar, K.; Frost, R. T.

    1982-01-01

    The electromagnetic levitation technique has been used to obtain nearly stoichiometric SmCo5, with the reaction temperature controlled by a gas jet. The results of several experiments carried out at a 450 kHz, 25 kw RF power levitation facility using different reaction times and cooling rates are presented. It is shown that reaction rates achieved with the levitation technique are larger than the expected diffusion rate in the system liquid samarium-solid cobalt. It is also shown that substantial mixing occurs in the RF-levitated melt.

  13. Reaction of Water-Saturated Supercritical CO2 with Forsterite: Evidence for Magnesite Formation at Low Temperatures

    SciTech Connect

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Z.; Hu, Mary Y.; Schaef, Herbert T.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O saturated supercritical CO2 (scCO2) at 35 C and 50 C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray Spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3.3H2O) and magnesite (MgCO3) at short reaction times ({approx}3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 C) than previously thought needed to overcome its well known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  14. Reaction of water-saturated supercritical CO2 with forsterite: Evidence for magnesite formation at low temperatures

    NASA Astrophysics Data System (ADS)

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Zhi; Hu, Mary; Todd Schaef, H.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O-saturated supercritical CO2 (scCO2) at 35 °C and 50 °C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3·3H2O) and magnesite (MgCO3) at short reaction times (˜3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 °C) than previously thought needed to overcome its well-known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 °C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  15. Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

    NASA Astrophysics Data System (ADS)

    Sanibondi, Paolo

    2015-09-01

    Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

  16. Formation of 2,5-dimethyl-4-hydroxy-3(2H)-furanone through methylglyoxal: a Maillard reaction intermediate.

    PubMed

    Wang, Yu; Ho, Chi-Tang

    2008-08-27

    The caramel-like aroma compound, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF) was quantified and verified by HPLC and GC-MS in the Maillard reaction based on methylglyoxal (MG). The reaction was performed in the 0.5 M phosphate buffer by heating MG with or without either glycine or cysteine at 120 degrees C for 1 h. MG alone or MG with cysteine could produce increased level of DMHF with pH increased, whereas MG with glycine had contrary trend. Experiments using a 1:1 mixture of [(13)C6]glucose and [(12)C6]glucose indicate that in the presence of glycine or cysteine, glucose skeleton kept intact during DMHF formation since a 1:1 mixture of [(13)C6]DMHF and [(12)C6]DMHF was formed. Acetylformoin was detected in the glucose with amino acid reaction system as a precursor of DMHF, while in the MG reaction systems, acetylformoin could not be identified. It is suggested different pathways of DMHF formation via MG and glucose. PMID:18593173

  17. The colorants, antioxidants, and toxicants from nonenzymatic browning reactions and the impacts of dietary polyphenols on their thermal formation.

    PubMed

    Zhang, Xinchen; Tao, Ningping; Wang, Xichang; Chen, Feng; Wang, Mingfu

    2015-02-01

    Nonenzymatic browning reactions proceed with the starting reactants of sugar and/or protein during thermal processing and storage of food. In addition to food color formation, the process also contributes to the loss of essential nutrients, generation of beneficial antioxidants, and production of toxicants, including 5-hydroxymethylfurfural (5-HMF), reactive carbonyl species, advanced glycation end products (AGEs), and heterocyclic amines (HAs). Recent research has demonstrated that dietary polyphenols can actively participate in nonenzymatic browning reactions, contributing to the generation of new colorants and antioxidants. More importantly, polyphenol addition has been found to be an effective approach to mitigate heat-induced formation of toxicants, mainly through inhibiting oxidative pathways and trapping reactive intermediates. In the matrix of polyphenol-fortified foods, a complex array of chemical interactions happen among polyphenols, traditional nutritional components, and neo-formed compounds they are thermally converted to. These reactions play a significant role in the colorants, antioxidants as well as toxicants production. Our findings support the potential of dietary polyphenols for increasing the antioxidant content and for reducing the level of toxicants when they participate in nonenzymatic browning reactions in fortified food products. PMID:25468403

  18. A kinetic study on the potential of a hybrid reaction mechanism for prediction of NOx formation in biomass grate furnaces

    NASA Astrophysics Data System (ADS)

    Zahirović, Selma; Scharler, Robert; Kilpinen, Pia; Obernberger, Ingwald

    2011-10-01

    This paper presents the verification of a hybrid reaction mechanism (28 species, 104 reactions) by means of a kinetic study with a view to its application for the CFD-based prediction of gas phase combustion and NOx formation in biomass grate furnaces. The mechanism is based on a skeletal kinetic scheme that includes the subsets for H2, CO, NH3 and HCN oxidation derived from the detailed Kilpinen 97 reaction mechanism. To account for the CH4 breakdown two related reactions from the 4-step global mechanism for hydrocarbons oxidation by Jones and Lindstedt were adopted. The hybrid mechanism was compared to the global mechanism and validated against the detailed Kilpinen 97 mechanism. For that purpose plug flow reactor simulations at conditions relevant to biomass combustion (atmospheric pressure, 1200-1600 K) for approximations of the flue gases in a grate furnace at fuel lean and fuel rich conditions were carried out. The hybrid reaction mechanism outperformed the global one at all conditions investigated. The most striking differences obtained in predictions by the hybrid and the detailed mechanism at the residence times prior to ignition were attributed to the simplified description of the CH4 oxidation in the case of the former. The overall agreement regarding both combustion and NOx chemistry between the hybrid and the detailed mechanism was better at fuel lean conditions than at fuel rich conditions. However, also at fuel rich conditions, the agreement was improving with increasing temperature. Moreover, it was shown that an improvement in the prediction of NOx formation by the N-subset of the hybrid reaction mechanism can be achieved by replacing its C-H-O subset with that of the detailed one.

  19. Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation.

    PubMed

    De Vera, Glen Andrew; Stalter, Daniel; Gernjak, Wolfgang; Weinberg, Howard S; Keller, Jurg; Farré, Maria José

    2015-12-15

    When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions. PMID:26378731

  20. An investigation of molybdenum and molybdenum oxide catalyzed hydrocarbon formation reactions

    SciTech Connect

    Tysoe, W.T.

    1995-09-01

    The document is divided into: experiments on model catalysts at high pressure, reaction studies on metallic Mo, surface chemistry experiments (metallic surfaces in ultrahigh vacuum; Mo(CO){sub 6} adsorption on alumina), and theoretical calculations.

  1. Mechanisms of branching reactions in melanin formation - Ab initio quantum engineering approach -

    NASA Astrophysics Data System (ADS)

    Kishida, Ryo; Menez Aspera, Susan; Kasai, Hideaki

    Melanin, a pigment found in animals, consists of two types of oligomeric unit: eumelanin and pheomelanin. The color of the skin, the hair, and the eyes is controlled by the ratio of eumelanin/pheomelanin production. Especially, dopachrome and dopaquinone are the precursor molecules of melanin which directly affect the composition of melanin through their branching reactions. Dopachrome is converted into two possible monomers of eumelanin. Dopaquinone can undergo both eumelanin and pheomelanin synthesis. To understand the mechanisms and controlling factors that govern the conversions, reactions of the two molecules are investigated using density functional theory-based first-principles calculations. Our results deepen mechanistic understanding of the reactions and open possibilities to design properties and functions of melanin. In this talk, we will discuss about the competitions of the branching reactions.

  2. Clear Zone Formation around Screws in the Early Postoperative Stages after Posterior Lumbar Fusion Using the Cortical Bone Trajectory Technique

    PubMed Central

    Iwatsuki, Koichi; Ohnishi, Yu-Ichiro; Ohkawa, Toshika; Yoshimine, Toshiki

    2015-01-01

    Study Design Retrospective study. Purpose To evaluate the initial fixation using the cortical bone trajectory (CBT) technique for posterior lumbar fusion through assessment of the clear zones around the screws and the risk factors involved. Overview of Literature Postoperative radiolucent zones (clear zones) are an indicator of poor conventional pedicle screw fixation. Methods Between January 2013 and April 2014, 19 patients (8 men and 11 women) underwent posterior lumbar interbody fusion or posterior lumbar fusion using the CBT technique. A total of 109 screws were used for evaluation with measurement of the maximum insertional torque of last two screw rotations. Clear zone-positivity on plain radiographs was investigated 6 months after surgery. The relation between intraoperative insertional torque and clear zone-positivity was investigated by one-way analysis of variance. In addition, the correlation between clear zone-positivity and gender, age (<75 years old or >75 years old), or operative stabilization level (<2 or >3 vertebral levels) was evaluated using the chi-square test. Results Clear zones were observed around six screws (5.50%) in five patients (26.3%). The mean insertional torque (4.00±2.09 inlbs) of clear zone-positive screws was lower than that of clear zone-negative screws (8.12±0.50 in-lbs), but the difference was not significant. There was a significant correlation between clear zone-positivity and operative level of stabilization. Conclusions The low incidence of clear zone-positive screws indicates good initial fixation using the CBT technique. Multilevel fusions may be risk factors for clear zone generation. PMID:26713120

  3. Biannual otolith-zone formation of young shallow-water hake Merluccius capensis in the northern Benguela: age verification using otoliths sampled by a top predator.

    PubMed

    Wilhelm, M R; Roux, J-P; Moloney, C L; Jarre, A

    2015-07-01

    Otoliths collected at least monthly from scat samples of Cape fur seals Arctocephalus pusillus are used to show that shallow-water hake Merluccius capensis from the northern Benguela develop three translucent zones in their first 1·5 years of life. The novel sampling approach provided otoliths that belonged to four M. capensis cohorts of approximate known age (hatched in 1996, 1998, 2002 and 2005), allowing age verification. Following spawning in austral winter, translucent zones consistently formed first in summer and autumn (T1), then in winter and spring (T2) and again in summer and autumn (T3), with no difference in appearance of the zones (biannuli) for the four cohorts considered. The second translucent zone is usually the first true annulus (year mark). It forms during July to September in fish of 15-20 cm total length (LT ). Formation of the translucent zones appears to be determined by fish length or age, rather than by exogenous cues. It is suggested that length measurements should be used to help determine the first age group; fish with a translucent zone marked at otolith lengths >7·5 mm should be termed 1 year-old fish. Ages of M. capensis used in previous stock assessment models have been overestimated. Biannuli are an unusual occurrence in fish otoliths in general, but have been observed in other Merluccius species. PMID:25990746

  4. In-place oil shale resources of the Mahogany zone sorted by grade, overburden thickness and stripping ratio, Green River Formation, Piceance Basin, Colorado and Uinta Basin, Utah

    USGS Publications Warehouse

    Birdwell, Justin E.; Mercier, Tracey J.; Johnson, Ronald C.; Brownfield, Michael E.

    2015-01-01

    A range of geological parameters relevant to mining oil shale have been examined for the Mahogany zone of the Green River Formation in the Piceance Basin, Colorado, and Uinta Basin, Utah, using information available in the U.S. Geological Survey Oil Shale Assessment database. Basinwide discrete and cumulative distributions of resource in-place as a function of (1) oil shale grade, (2) Mahogany zone thickness, (3) overburden thickness, and (4) stripping ratio (overburden divided by zone thickness) were determined for both basins on a per-acre basis, and a resource map showing the areal distribution of these properties was generated. Estimates of how much of the Mahogany zone resource meets various combinations of these parameters were also determined. Of the 191.7 billion barrels of Mahogany zone oil in-place in the Piceance Basin, 32.3 percent (61.8 billion barrels) is associated with oil shale yielding at least 25 gallons of oil per ton (GPT) of rock processed, is covered by overburden 1,000 feet thick or less, and has a stripping ratio of less than 10. In the Uinta Basin, 14.0 percent (29.9 billion barrels) of the 214.5 billion barrels of Mahogany zone oil in-place meets the same overburden and stripping ratio criteria but only for the lower grade cutoff of 15 GPT.

  5. Kinetic Modeling of Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Formation Based on Carbon Degradation Reactions

    EPA Science Inventory

    Combustion experiments in a laboratory-scale fixed bed reactor were performed to determine the role of temperature and time in PCDD/F formation allowing a global kinetic expression to be written for PCDD/F formation due to soot oxidation in fly ash deposits. Rate constants were c...

  6. Zone separator for multiple zone vessels

    DOEpatents

    Jones, John B.

    1983-02-01

    A solids-gas contact vessel, having two vertically disposed distinct reaction zones, includes a dynamic seal passing solids from an upper to a lower zone and maintaining a gas seal against the transfer of the separate treating gases from one zone to the other, and including a stream of sealing fluid at the seal.

  7. Effects of fruit extracts on the formation of acrylamide in model reactions and fried potato crisps.

    PubMed

    Cheng, Ka-Wing; Shi, Jian-Jun; Ou, Shi-Yi; Wang, Mingfu; Jiang, Yue

    2010-01-13

    Natural products extracted from plants and fruits have attracted increasing attention for the development of effective inhibitors against the formation of acrylamide during food processing. In this study, six fruit extracts (apple, blueberry, mangosteen, longan, dragon fruit with white flesh, and dragon fruit with red flesh) were compared for their activities against acrylamide formation in chemical models containing equal molar quantities of glucose and asparagine in distilled water (160 degrees C for 30 min). Apple extract demonstrated potent inhibition on acrylamide formation. Blueberry, mangosteen, and longan extracts did not have significant impact, whereas dragon fruit extracts enhanced acrylamide formation. Column chromatography guided by chemical model analysis showed that the proanthocyanidin-rich subfraction played a key role in mediating the inhibitory activity. The inhibitory activity was finally corroborated in fried potato crisps. The present study identified some natural products that might have important applications in the food industry to inhibit acrylamide formation. PMID:19925016

  8. Evolution of crustal stress, pressure and temperature around shear zones during orogenic wedge formation: a 2D thermo-mechanical numerical study

    NASA Astrophysics Data System (ADS)

    Markus Schmalholz, Stefan; Jaquet, Yoann

    2016-04-01

    We study the formation of an orogenic wedge during lithospheric shortening with 2D numerical simulations. We consider a viscoelastoplastic rheology, thermo-mechanical coupling by shear heating and temperature-dependent viscosities, gravity and erosion. In the initial model configuration there is either a lateral temperature variation at the model base or a lateral variation in crustal thickness to generate slight stress variations during lithospheric shortening. These stress variations can trigger the formation of shear zones which are caused by thermal softening associated with shear heating. We do not apply any kind of strain softening, such as reduction of friction angle with progressive plastic strain. The first major shear zone that appears during shortening crosscuts the entire crust and initiates the asymmetric subduction/underthrusting of mainly the mechanically strong lower crust. After some deformation, the first shear zone in the upper crust is abandoned, the deformation propagates towards the foreland and a new shear zone forms only in the upper crust. The shear zone propagation occurs several times where new shear zones form in the upper crust and the mechanically strong top of the lower crust acts as detachment horizon. We calculate the magnitudes of the maximal and minimal principal stresses and of the mean stress (or dynamic pressure), and we record also the temperature for several marker points in the upper and lower crust. We analyse the evolution of stresses and temperature with burial depth and time. Deviatoric stresses (half the differential stress) in the upper crust are up to 200 MPa and associated shear heating in shear zones ranges between 40 - 80 °C. Lower crustal rocks remain either at the base of the orogenic wedge at depths of around 50 km or are subducted to depths of up to 120 km, depending on their position when the first shear zone formed. Largest deviatotric stresses in the strong part of the lower crust are about 1000 MPa and

  9. Geochemical signature and transfers in the Vadose zone of a geological carbonate formation : example of an underground quarry, Gironde, France

    NASA Astrophysics Data System (ADS)

    Loisy, C.; Franceschi, M.; Cerepi, A.; Mao, L.

    2007-12-01

    The aim of this study is to understand physico-chemical weathering processes in the vadose zone. The study combines hydrogeological and hydrogeochemical data on pore water with information about solid phase composition of the unsaturated zone. A monitoring station in the vadose zone is established in the Oligocene Aquitain limestone : the soil (0.40 meter thick) is lies on the Oligocene limestone (30 meters thick). The water table is 19.80 m average. A borehole with a diameter of 0.8 m is instrumented with "Teflon- quartz" cells (for the sampling of the pore water), with TDR probes (Time Domain Reflectometry) and SP (Self-Potential) electrodes (to measure the water content of the porous rock) and that all along the unsaturated zone. Chemically, the pH, alkalinity and the content of cations and anions are measured. The contents of cations and anions show variations with the depth. Results of chemical water analysis show that the unsaturated zone can be devided in three zones where the equilibrum of the calco-carbonic system can be moved with the precipitation or dissolution of dominating phenomena. The shallow zone down to a depth of seven meters corresponds to a zone with a significant decrease of mineralization (calcium, magnesium, sulfate) and evapotranspiration dynamic water. The second zone between seven to sixteen meters displays a high stability. The third zone (zone of capillary fringe) between sixteen to twenty meter shows a rise of certain ionic concentrations. The saturation index for the calcite calculated from PHREEQC program as a function of depth gives both dissolution/precipitation processes in the carbonate rock.

  10. Formation Of Cometary Hydrocarbons By Hydrogen Addition Reactions On Cold Grains

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hitomi; Watanabe, N.; Kawakita, H.; Fukushima, T.

    2012-10-01

    Hydrogen addition reactions on cold grains are considered to play an important role to form many kinds of volatiles in low temperature conditions like molecular clouds or early solar nebula. We can investigate the physical conditions (e.g., temperature, gas density, and etc.) of the early solar nebula via chemical properties of the pristine bodies like comets. The hydrocarbons like C2H2 and C2H6 have been studied so far and C2H6 might be a product of successive hydrogen addition of C2H2 on the cold grain. To evaluate the efficiency of hydrogen addition reactions from C2H2 to C2H6 quantitatively, we conducted laboratory measurements of those reactions under multiple conditions of the samples (on H2O ice) at different temperatures (10, 20, 30 K) with the LASSIE apparatus at Hokkaido University. Our results provide more detailed information about those reactions than previous quantitative studies. We discuss about the reaction rates with different samples and conditions.

  11. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  12. Formation of pseudomorphic nanocages from Cu2O nanocrystals through anion exchange reactions.

    PubMed

    Wu, Hsin-Lun; Sato, Ryota; Yamaguchi, Atsushi; Kimura, Masato; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu

    2016-03-18

    The crystal structure of ionic nanocrystals (NCs) is usually controlled through reaction temperature, according to their phase diagram. We show that when ionic NCs with different shapes, but identical crystal structures, were subjected to anion exchange reactions under ambient conditions, pseudomorphic products with different crystal systems were obtained. The shape-dependent anionic framework (surface anion sublattice and stacking pattern) of Cu2O NCs determined the crystal system of anion-exchanged products of CuxS nanocages. This method enabled us to convert a body-centered cubic lattice into either a face-centered cubic or a hexagonally close-packed lattice to form crystallographically unusual, multiply twinned structures. Subsequent cation exchange reactions produced CdS nanocages while preserving the multiply-twinned structures. A high-temperature stable phase such as wurtzite ZnS was also obtained with this method at ambient conditions. PMID:26989249

  13. Zwitterion formation in titan ice analogs: reaction between HC3N and NH3.

    PubMed

    Couturier-Tamburelli, Isabelle; Sessouma, Bintou; Chiavassa, Thierry; Piétri, Nathalie

    2012-11-01

    A zwitterion is formed in the laboratory at low temperatures in the solid phase from the thermal reaction of HC(3)N and NH(3). We report for the first time its infrared spectrum. We study its reaction using Fourier transform infrared spectroscopy. Its reaction rate is estimated to be k(T) = 2.9 × 10(5) exp(-2.3 ± 0.1 (kJ mol(-1))/RT). Calculations using density functional theory (B3LYP/6-31g**) are used to characterize all the species (complexes, zwitterions, and transition states) and are in good agreement with the infrared spectra. The structure of the zwitterion is determined planar and it is characterized by a N-C bond around 1.5 Å. PMID:23075265

  14. Polymer immobilized Cu(I) formation and azide-alkyne cycloaddition: A one pot reaction

    PubMed Central

    Islam, Rafique Ul; Taher, Abu; Choudhary, Meenakshi; Siwal, Samarjeet; Mallick, Kaushik

    2015-01-01

    During the polymerization of aniline using copper sulphate, act as an oxidizing agent, the in-situ synthesized Cu(I) ion catalyzed the cyclo-addition between azides and alkynes. This work represents the merging of two steps, synthesis of the catalyst and application of the catalyst, in a one pot reaction. The elimination of the separate catalyst synthesis step is economic in terms of cost and time. As aniline was used as one of the reactant components so there is no requirement to use additional base for this reaction that further eliminates the cost of the process. Again, the catalyst can be readily recovered by filtration and efficiently used for the several sets of reactions without any significant loss of catalytic activity. PMID:25966018

  15. Bifunctional mechanism of catalysis in reactions leading to formation of /alpha/-amino ketones

    SciTech Connect

    Popov, A.F.; Anikeev, A.V.

    1988-10-20

    The kinetics of the reaction of /alpha/-bromoacetophenone and benzyl bromide with aniline and pyridine in the presence of additions of acetic acid and phenol in benzene at 30/degree/C were investigated. The catalytic effects due to the activity of the uncombined forms of the catalyst, their dimers, and their 1:1 complexes with the amines were separated quantitatively. The change in the catalytic activity of the respective particles in the solutions with variation in the structure of the reagents is examined, and possible mechanisms for the catalytic reactions are discussed on this basis. It is concluded that there is a bifunctional mechanism of catalysis by acetic acid in the reaction of /alpha/-bromoacetophenone with aniline.

  16. Reactions of a Dinitrogen Complex of Molybdenum: Formation of a Carbon-Nitrogen Bond.

    ERIC Educational Resources Information Center

    Busby, David C.; And Others

    1981-01-01

    Reports a procedure for the formation of alkyldiazenido complexes of molybdenum in the absence of dioxygen, suitable for inclusion in an advanced inorganic chemistry laboratory. Includes background information and experimental procedures for two complexes. (SK)

  17. Investigation of reaction kinetics and interfacial phase formation in Ti3Al + Nb composites

    NASA Technical Reports Server (NTRS)

    Wawner, F. E.; Gundel, D. B.

    1992-01-01

    Titanium aluminide metal matrix composites are prominent materials systems being considered for high temperature aerospace applications. One of the major problems with this material is the reactivity between existing reinforcements and the matrix after prolonged thermal exposure. This paper presents results from an investigation of reaction kinetics between Ti-14Al-21Nb (wt pct) and SCS-6 fibers and SiC fibers with surface coatings of TiB2, TiC, TiN, W, and Si. Microstructural evaluation of the reaction layers as well as matrix regions around the fibers is presented.

  18. Systematic study of quasifission characteristics and timescales in heavy element formation reactions

    NASA Astrophysics Data System (ADS)

    Hinde, D. J.; Williams, E.; Mohanto, G.; Simenel, C.; Dasgupta, M.; Wakhle, A.; Carter, I. P.; Cook, K. J.; Jeung, D. Y.; Luong, D. H.; Palshetkar, C. S.; Prasad, E.; Rafferty, D. C.; du Rietz, R.; Simpson, E. C.

    2016-05-01

    Superheavy elements can only be created in the laboratory by the fusion of two massive nuclei. Mass-angle distributions give the most direct information on the characteristics and time scales of quasifission, the major competitor to fusion in these reactions. The systematics of 42 mass-angle distributions provide information on the global characteristics of quasifission. Deviations from the systematics reveal the major role played by the nuclear structure of the two colliding nuclei in determining the reaction outcome, and in hindering or favouring heavy element production.

  19. Astrophysical reaction rate for Be9 formation within a three-body approach

    NASA Astrophysics Data System (ADS)

    Casal, J.; Rodríguez-Gallardo, M.; Arias, J. M.; Thompson, I. J.

    2014-10-01

    The structure of the Borromean nucleus Be9 (α+α+n) is addressed within a three-body approach using the analytical transformed harmonic oscillator method. The three-body formalism provides an accurate description of the radiative capture reaction rate for the entire temperature range relevant in astrophysics. At high temperatures, results match the calculations based on two-step sequential processes. At low temperatures, where the particles have no access to intermediate two-body resonances, the three-body direct capture leads to reaction rates larger than the sequential processes. These results support the reliability of the method for systems with several charged particles.

  20. Deep-space glycine formation via Strecker-type reactions activated by ice water dust mantles. A computational approach.

    PubMed

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2010-01-01

    A Strecker-type synthesis of glycine by reacting NH(3), H(2)C=O and HCN in presence of ice water (H(2)O-ice) as a catalyst has been theoretically studied at B3LYP/6-31+G(d,p) level within a cluster approach in order to mimic reactions occurring in the interstellar and circumstellar medium (ICM). Results indicate that, despite the exoergonic character of the considered reactions occurring at the H(2)O-ice surface, the kinetics are slow due to relatively high electronic energy barriers (ΔU(0)(≠)=15-45 kcal mol(-1)). Reactions occurring within H(2)O-ice cavities, in which ice bulk effects have been modeled by assuming a dielectric continuum (ε=78), show energy barriers low enough to allow NH(2)CH(2)OH formation but not NH=CH2 (ΔU(0)(≠)= 2 and 21 kcal mol(-1), respectively) thus hindering the NH(2)CH(2)CN formation, i.e. the precursor of glycine, through Strecker channels. Moreover, hydrolysis of NH(2)CH(2)CN to give glycine is characterized by high electronic energy barriers (ΔU(0)(≠)=27-34 kcal mol(-1)) and cannot readily occur at cryogenic temperatures. Nevertheless, the facts that NH=CH(2) formation can readily be achieved through the radical-radical HCN+2H - NH−−>CH2 reaction [D. E. Woon, Astrophys. J., 2002, 571, L177-L180], and that present results indicate that the Strecker step of NH=CH(2)+HCN−−>NH(2)CH(2)CN exhibits a relative low energy barrier (ΔU(0)(≠)=8–9 kcal mol(-1)), suggest that a combination of these two mechanisms allows for the formation of NH(2)CH(2)CN in the ICM. These results strengthen the thesis that NH(2)CH(2)CN could have been formed and protected by icy dust particles, and then delivered through micro-bombardments onto the early Earth, leading to glycine formation upon contact with the primordial ocean. PMID:20358044

  1. Reaction zone between pre-UHP titanite and host rock: insights into fluid-rock interaction and deformation mechanisms during exhumation of deeply subducted continental crust (Dabie Shan UHP unit, China)

    NASA Astrophysics Data System (ADS)

    Wawrzenitz, N.; Romer, R. L.; Grasemann, B.; Morales, L. F. G.

    2012-04-01

    titanite grains are patchy zoned and replace, along with rutile, calcite, quartz, and apatite, the old titanite megacryst. This reaction reflects the changing CO2 versus fluorine activity in the available fluid phase, rather than changing P-T conditions. The Sr isotope composition of the phases formed by these fluid-mediated reactions is variable and depends on the reaction-history and origin of the fluids. (iii) Brittle deformation of the titanite megacryst induced the formation of fractures, enhancing fluid transport and precipitation of new titanite, allanite, calcite ± rutile, and albite (locally anorthite), as well as Zn(Fe) - and Cu - sulphides along the vein walls. Dislocation creep is indicated by subgrains in local zones of high differential stress within the rim of the titanite megacryst. However, dissolution precipitation creep has been much more effective in changing the (isotope)chemical composition of titanite compared to dislocation creep. Romer, R.L., Wawrzenitz, N., Oberhänsli, R., 2003. Terra Nova 15, 5, 330-336. Wawrzenitz, N., Romer, R.L., Oberhänsli, R., Dong, S., 2006. Lithos 89, 1-2, 174-201.

  2. The Formation of Secondary Organic Aerosol from the Isoprene + OH Reaction in the Absence of NOx

    EPA Science Inventory

    The reaction of isoprene (C5H8) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog ch...

  3. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  4. Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

    PubMed

    Thompson, Matthew G K; Parnis, J Mark

    2005-10-27

    The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene. PMID:16866395

  5. Secondary organic aerosol formation from the gas phase reaction of hydroxyl radicals with m-, o- and p-cresol

    NASA Astrophysics Data System (ADS)

    Henry, Françoise; Coeur-Tourneur, Cecile; Ledoux, Frédéric; Tomas, Alexandre; Menu, Dominique

    Secondary organic aerosol (SOA) formation during the atmospheric oxidation of cresols was investigated using a large smog chamber (8000 L), at atmospheric pressure, 294±2 K and low relative humidity (6-10%). Cresol oxidation was initiated by irradiation of cresol/CH 3ONO/NO/air mixtures. The cresol loss was measured by gas chromatography with a flame ionization detector (GC-FID) and the temporal evolution of the aerosol was monitored using a scanning mobility particle sizer (SMPS). The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted cresol concentrations assuming a particle density of 1.4 g cm -3. Analysis of the data clearly show that Y is a strong function of Mo and that SOA formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial cresol concentration, which leads to aerosol yields from 9% to 42%. These results are in good agreement with a recent study performed on SOA formation from the photo-oxidation of o-cresol in a smog chamber. To our knowledge, the present work represents the first investigation of SOA formation from OH reaction with m- and p-cresol.

  6. A quantum chemical topological analysis of the C-C bond formation in organic reactions involving cationic species.

    PubMed

    Domingo, Luis R; Pérez, Patricia

    2014-07-21

    ELF topological analysis of the ionic Diels-Alder (I-DA) reaction between the N,N-dimethyliminium cation and cyclopentadiene (Cp) has been performed in order to characterise the C-C single bond formation. The C-C bond formation begins in the short range of 2.00-1.96 Åvia a C-to-C pseudoradical coupling between the most electrophilic center of the iminium cation and one of the two most nucleophilic centers of Cp. The electron density of the pseudoradical center generated at the most electrophilic carbon of the iminium cation comes mainly from the global charge transfer which takes place along the reaction. Analysis of the global reactivity indices indicates that the very high electrophilic character of the iminium cation is responsible for the negative activation energy found in the gas phase. On the other hand, the analysis of the radical P(k)(o) Parr functions of the iminium cation, and the nucleophilic P(k)(-) Parr functions of Cp makes the characterisation of the most favourable two-center interaction along the formation of the C-C single bond possible. PMID:24901220

  7. Statistical characterisation and stochastic parameterisation of sedimentary geological formations on their reaction capacity for sustainable groundwater quality management

    NASA Astrophysics Data System (ADS)

    Griffioen, J.; Vermooten, S.; Keijzer, T.; Bakr, M.; Valstar, J.

    2012-04-01

    The fate of contaminants in groundwater aquifers is determined by the buffering capacity of those aquifers together with the composition of inflowing groundwater. A nationwide characterisation of the environmental geochemistry of the shallow subsurface (down to 30 m below surface) has been started in the Netherlands. This covers: 1. the reaction capacity of sediments as buffer for contamination, and 2. typical elemental composition of geological formations and the association between trace elements and major minerals. For this purpose, the Netherlands is subdivided into 27 so-called geotop regions each having a unique geological build-up of the shallow subsurface. Here, four types are recognised based on vertical hydrogeological build-up. The regions are statistically characterised on their geochemical composition using combinations of lithological class and geological formation as strata. The statistical data are subsequently coupled with a geological voxel model of the subsurface to stochastically parameterise the geological units on reaction capacity. This combined approach will be illustrated for the Dutch province Zeeland. Reaction capacity is considered as a series of geochemical characteristics that control acid/base condition, redox condition and sorption capacity. Five primary reaction capacity variables are characterised: 1. pyrite, 2. non-pyrite, reactive iron (oxides, siderite and glauconite), 3. clay fraction, 4. organic matter and 5. Ca-carbonate. Important reaction capacity variables that are determined by more than one solid compound are also deduced: 1. potential reduction capacity (PRC) by pyrite and organic matter, 2. cation-exchange capacity (CEC) by organic matter and clay content, 3. carbonate buffering upon pyrite oxidation (CPBO) by carbonate and pyrite. A statistical investigation of several hunderds of sediment analyses is performed that provides the geochemical properties of the sediments. Here, classification based on sedimentary facies

  8. Contemporary surface ruptures in the zone of the Baikal-Mondy fault (Baikal rift system): dynamics of formation and origin

    NASA Astrophysics Data System (ADS)

    Sankov, Vladimir; Sankov, Aleksei; Lebedeva, Marina; Ashurkov, Sergey; Parfeevets, Anna

    2014-05-01

    .08.2008, Mw = 6.3), the epicenter of which was located near the southern tip of the Baikal basin. The existence of centimeter level deformations is confirmed using of differential SAR interferometry method. A pair of images taken with an interval of 2 years highlighted the linear zone of active deformation in the centimeter level. The length of the structure is about 4 kilometers. The offset along the Line-of-Sight (LOS) direction is from 18 to 42 mm, which corresponds to the vertical displacement of 22 to 50 mm, or a horizontal displacement of 32 to 74 mm (Lebedeva et al., 2013). Along with the described ruptures we discovered normal faults with an amplitude greater than 2 m, which can be traced along the submeridional local watershed. The length of the normal faults reaches 800 m. The morphology and position of these faults can be attributed to their sackung structures. We conclude that the detected current surface ruptures have complex origins and develop under the influence of endogenous (tectonic) and exogenous forces. They founded along NE trending ancient tectonic structures within wide strike-slip zone and main direction of opening corresponds to the direction of extension of paleo- and present-day stress field. According to the dynamics of ruptures opening, the main phase of their formation is connected with stage of Kultuk earthquake preparation. As for geodetic data the block is stretched in all directions, it can be assumed that, by analogy with closely spaced sacking

  9. Permeability of a fault zone crosscutting a sequence of sandstones and shales and its influence on hydraulic head distribution in the Chatsworth Formation, California, USA

    NASA Astrophysics Data System (ADS)

    Cilona, Antonino; Aydin, Atilla; Johnson, Nicholas M.

    2015-03-01

    Faults influence groundwater flow paths. The transport of groundwater contaminants within the faulted sandstones and shales of Chatsworth Formation exposed in southern California, USA, have been investigated. Structural and hydrogeological data are combined to interpret the hydraulic-head drop measured across a fault with tens of meters of oblique-slip. The fault zone architecture was delineated at two locations: an outcrop and a borehole intersecting the fault at depth. At the first station, the fault juxtaposes sandstones against shales with a fault core mostly consisting of deformed shale. A series of shale beds striking parallel to the fault zone and dipping ˜50° toward the fault zone provides evidence that the shale was incorporated into the fault zone. At the second station, borehole images show a plane juxtaposing fractured sandstone against shale-rich fault rock. Hydraulic heads measured at 30 wells show a drop of 75 m across the fault, which is interpreted to be a result of the low-permeability shaley fault rock. It is proposed that the shale was incorporated into the fault zone by shale smearing. These results are consistent with numerical modeling, which requires a low-permeability fault core to simulate the observed hydraulic head differences. Understanding the hydraulic nature of this fault provides a critical constraint for evaluating the future migration of contaminants in the groundwater system.

  10. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+]) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of the photooxidation products and the sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (8 groups) and aerosol phase reactivity (6 groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid catalyzed reactions, and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx. The model is validated using isoprene photooxidation experiments performed in the dual, outdoor UF APHOR chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total OM formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC, and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and

  11. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

  12. Lens proteins block the copper-mediated formation of reactive oxygen species during glycation reactions in vitro.

    PubMed

    Ortwerth, B J; James, H L

    1999-06-16

    The formation of advanced glycation endproducts (AGEs) from glucose in vitro requires both oxygen and a transition metal ion, usually copper. These elements combine to produce reactive oxygen species (ROS) which degrade glucose to AGE-forming compounds. We measured the ability of Cu(2+) to accelerate ROS formation, and the effect of added lens proteins on these reactions. Increasing levels of Cu(2+) accelerated the formation of superoxide anion with glucose and fructosyl-lysine, but the addition of 2.0 mg/ml calf lens proteins completely blocked superoxide formation up to 100 microM of added Cu(2+). Lens proteins, however, had no effect on superoxide generated by the hypoxanthine/xanthine oxidase system. The oxidation of ascorbic acid was increased 170-fold by the addition of 10 microM Cu(2+), but was also completely prevented by added lens proteins. Hydroxyl radical formation, as measured by the conversion of benzoate to salicylate, was increased to 30 nmoles/ml after 18 h by the addition of 100 microM Cu(2+) and 2.5 mM H2O2. This increase was also blocked by the addition of lens proteins. However, hydroxyl radical formation, as estimated by the crosslinking and fragmentation of lens proteins, was observed in the presence of 100 microM Cu(2+), likely at the sites of Cu(2+) binding. Since the ratio of lens proteins to Cu(2+) in human lens is at least 1000-fold higher than those used here, the data argue that Cu(2+) in the lens would be tightly bound to protein, preventing ROS-mediated AGE formation from glucose in vivo. PMID:10364483

  13. Deciphering Timescales and Mechanisms of Mineral Reactions During Exhumation Processes Using Element Zoning in Exsolution Lamellae in a Garnet Pyroxenite From the Granulitgebirge in Saxony, Germany

    NASA Astrophysics Data System (ADS)

    Muller, T.; Massonne, H.; Willner, A. P.

    2013-12-01

    Si can be rather related to the growth history of the lamellae. For example, preliminary modeling results of the Fe-Mg exchange suggest very efficient compositonal resetting even for very fast cooling rates at high temperatures, so that no record of the growth of the lamellae is preserved above 1000 °C. Nevertheless, the presence of slight chemial zoning can successfully be used to estimate P-T conditions of lamellae formation as well as cooling / exhumation rates in the temperature range between 700 - 1000 °C. Finally, modeling results indicate fast cooling rates of >> 100 °C/Ma in agreement with published estimates for the exhumation of the crystalline complex of the Granulitgebirge.

  14. [Formation of a generalized reaction of choice of object according to color in a young chimpanzee].

    PubMed

    Kuznetsova, T G; Syrenskiĭ, V I

    1987-01-01

    It has been established that the necessary conditions for rapid formation of experience in chimpanzees are creation of the interspecific functional system experimenter-chimpanzee in which the mechanisms of imitation and refreshment and creation of situational conditional reflex may be equally used. The neurophysiological basis of the latter is the stage activity when each stage is the signal for the following and refreshment for the previous one. In the presence of these factors the possibility of formation of aim generalized reflex appears, that is the basis for creation of optimum conditions for perception and learning the given information. PMID:3663771

  15. Formation and reactions of paramagnetic species in irradiated microheterogeneous copolymer systems with different electronic characteristics of components

    NASA Astrophysics Data System (ADS)

    Zezin, A. A.; Feldman, V. I.

    2002-01-01

    The formation of paramagnetic species in the radiolysis of styrene-butadiene block copolymers and interpolymers of polystyrene and polytrichlorobutadiene was studied at 77 K using ESR spectroscopy. The results obtained reveal substantial non-additive effects in the radical yields. In the case of interpolymers, the observed yields are higher than the expected additive values (sensitization), whereas in the case of block copolymers the effect has the opposite sign (protection). The analysis of paramagnetic species demonstrates that the observed peculiarities result from interphase migration of electrons followed by their reactions with chemical traps (chlorinated groups or neutral radicals). It was concluded that the long-range reactions of electrons were controlled by electronic characteristics of microphases.

  16. 'Would you eat cultured meat?': Consumers' reactions and attitude formation in Belgium, Portugal and the United Kingdom.

    PubMed

    Verbeke, Wim; Marcu, Afrodita; Rutsaert, Pieter; Gaspar, Rui; Seibt, Beate; Fletcher, Dave; Barnett, Julie

    2015-04-01

    Cultured meat has evolved from an idea and concept into a reality with the August 2013 cultured hamburger tasting in London. Still, how consumers conceive cultured meat is largely an open question. This study addresses consumers' reactions and attitude formation towards cultured meat through analyzing focus group discussions and online deliberations with 179 meat consumers from Belgium, Portugal and the United Kingdom. Initial reactions when learning about cultured meat were underpinned by feelings of disgust and considerations of unnaturalness. Consumers saw few direct personal benefits but they were more open to perceiving global societal benefits relating to the environment and global food security. Both personal and societal risks were framed in terms of uncertainties about safety and health, and possible adverse societal consequences dealing with loss of farming and eating traditions and rural livelihoods. Further reflection pertained to skepticism about 'the inevitable' scientific progress, concern about risk governance and control, and need for regulation and proper labeling. PMID:25541372

  17. Stabilized borata-alkene formation: structural features, reactions and the role of the counter cation.

    PubMed

    Kohrt, Sonja; Dachwitz, Steffen; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

    2015-12-28

    Dimethylbenzofulvene adds Piers' borane [HB(C6F5)2] at the indene double bond to give a mixture of regioisomeric boranes 8a,b. Subsequent isomerization under equilibrium conditions gives the isopropyl substituted 1H and 3H borylindenes 10a,b. Their treatment with the bulky LiTMP base under frustrated Lewis pair conditions resulted in a clean deprotonation reaction to give the borata-alkene 14. Its X-ray crystal structure analysis indicated a pronounced B[double bond, length as m-dash]C double bond character and thus a borata-benzofulvene description. The borata-alkene underwent (probably stepwise) [4 + 2] cycloaddition reactions with chalcone derivatives and a formal [6 + 2] cycloaddition with phenylmethylketene. Many products and derivatives were characterized by X-ray diffraction. PMID:26584629

  18. Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

    NASA Technical Reports Server (NTRS)

    Leu, M. T.; Lin, C. L.; Demore, W. B.

    1977-01-01

    The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

  19. Condensation reactions of guanidines with bis-electrophiles: Formation of highly nitrogenous heterocyclesa

    PubMed Central

    Arnold, David M.; LaPorte, Matthew G.; Anderson, Shelby M.; Wipf, Peter

    2013-01-01

    2-Amino-1,4-dihydropyrimidines were reacted with bis-electrophiles to produce novel fused bi-pyrimidine, pyrimido-aminotriazine, and pyrimido-sulfonamide scaffolds. In addition, a quinazoline library was constructed using a guanidine Atwal-Biginelli reaction with 1-(quinazolin-2-yl)guanidines. The product heterocycles have novel constitutions with high nitrogen atom counts and represent valuable additions to screening libraries for the discovery of new modulators of biological targets. PMID:23976798

  20. Formation of Thermally Robust Frustrated Lewis Pairs by Electrocyclic Ring Closure Reactions.

    PubMed

    Chen, Guo-Qiang; Kehr, Gerald; Daniliuc, Constantin G; Mück-Lichtenfeld, Christian; Erker, Gerhard

    2016-04-25

    The phosphorus/boron-substituted hexatriene systems 6 undergo thermally induced electrocyclic ring closure to yield the cyclohexadiene-derived P/B frustrated Lewis pairs (FLPs) 7. Subsequent TEMPO oxidation gives the phenylene-bridged FLPs 8. Both systems activate dihydrogen and the thermally robust FLPs undergo carbon-carbon coupling reactions at a mesityl group upon treatment with dimethyl acetylenedicarboxylate at elevated temperatures. PMID:27010753

  1. Formation of amorphous Fe 50Si 50 alloy by diffusion reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zhihua; Wang, Wenkui; Li, Jingfeng; Wang, Yuming

    1989-02-01

    The solid state reaction in the multilayer film with alternative polycrystalline Fe and amorphous Si layers has been studied with X-ray diffraction. Amorphous Fe 50Si 50 phase was formed after annealing isothermally at 300°C, which is explained in view of the consideration that an amorphous phase can be more favorable to form than a supersaturated solution in thermodynamics as well as than an equilibrium compound FeSi in kenetics.

  2. An expanded reaction kinetic model of the CuO surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol

    PubMed Central

    Khachatryan, Lavrent; Lomnicki, Slawo; Dellinger, Barry

    2014-01-01

    An expanded reaction kinetic model, including 17 surface reactions, is proposed to explain the yields of PCDD/F obtained in an experimental study of the reaction of 2-chlorophenol over a CuO/silica surface. The mechanism is loosely based on the gas-phase mechanism for PCDD/F formation widely discussed in the literature. The principal differences are the impact of chemisorption of 2-chlorophenols to metal oxides on radical formation and the steric hindrance of oxygen-centered radicals on the surface inhibiting radical–radical reaction pathways that lead to formation of dibenzo-p-dioxin (DD). Gas-phase molecule–surface-bound adsorbate reactions are the preferred route of DD formation, while radical–radical surface reactions are the main channel for dichloro-dibenzofuran (DCDF) formation. These results suggest that the Langmuir–Hinshelwood (LH) mechanism, involving radical–radical surface reactions, and the Eley–Rideal mechanism, involving a gas-phase molecule and surface-bound adsorbate, are responsible for PCDF and PCDD formation on surfaces, respectively. The calculated yields of DCDF and DD are in reasonable agreement with experimental results. PMID:17509655

  3. Formation of TEMPOL-hydroxylamine during reaction between TEMPOL and hydroxyl radical: HPLC/ECD study.

    PubMed

    Kudo, Wataru; Yamato, Mayumi; Yamada, Ken-Ichi; Kinoshita, Yuichi; Shiba, Takeshi; Watanabe, Toshiaki; Utsumi, Hideo

    2008-05-01

    Nitroxyl radicals are important antioxidants that have been used to protect animal tissues from oxidative damage. Their reaction with hydroxyl radical ((*)OH) is generally accepted to be the mechanism of antioxidant function. However, the direct interaction of nitroxyl radicals with (*)OH does not always provide a satisfactory explanation in various pH, because the concentration of hydrogen ion may affect the generation of secondary (*)OH-derived radicals. In the present study, it was confirmed that the reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) and (*)OH generated TEMPOL-hydroxylamine, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPON) and TEMPON-hydroxylamine using HPLC coupled with electrochemical detection. In the absence of NADH, TEMPOL-H may be generated by the reaction with secondary (*)OH-derived radicals in acidic condition. In the presence of NADH, a large proportion of the non-paramagnetic products was TEMPOL-H. Finally, it was clarified that TEMPOL-H was generated during dopamine metabolism, which is believed to be one of the (*)OH sources in pathological processes such as Parkinson's disease. PMID:18484414

  4. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32‑ ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  5. Formation of left-lateral fractures within the Summit Ridge shear zone, 1989 Loma Prieta, California, earthquake

    SciTech Connect

    Johnson, A.M.; Fleming, R.W. |

    1993-12-01

    The 1989 Loma Prieta, California, earthquake is characterized by the lack of major, throughgoing, coseismic, right-lateral faulting along strands of the San Andreas fault zone in the epicentral area. Instead, throughout the Summit Ridge area there are zones of tension cracks and left-lateral fracture zones oriented about N45 deg W, that is, roughly parallel to the San Andreas fault in this area. The left-lateral fractures zones are enigmatic because their left-lateral slip is opposite to the right-lateral sense of the relative motion between the Pacific and North American plates. We suggest that the enigmatic fractures can be understood if we assume that coesiesmic deformation was by right-lateral shear across a broad zone, about 0.5 km wide and 4 km long, beneath Summit Ridge. Contrary to most previous reports on the Loma Prieta earthquake, which assert that coseismic, right-lateral ground rupture was restricted to considerable (greater than 4 km) depths in the epicentral area, we find that nearly all the right-lateral offset is represented at the ground surface by the Summit Ridge shear zone.

  6. Interfacial Reaction-Driven Formation of Silica Carbonate Biomorphs with Subcellular Topographical Features and Their Biological Activity.

    PubMed

    Wang, Guocheng; Zhao, Xiaobing; Möller, Marco; Moya, Sergio E

    2015-10-28

    We report the interfacial reaction-driven formation of micro/nanostructured strontium carbonate (SrCO3) biomorphs with subcellular topographical features on strontium zinc silicate (Sr2ZnSi2O7) biomedical coatings and explore their potential use in bone tissue engineering. The resulting SrCO3 crystals build a well-integrated scaffold surface that not only prevents burst release of ions from the coating but also presents nanotopographical features similar to cellular filopodia. The surface with biomorphic crystals enhances osteoblast adhesion, upregulates the alkaline phosphatase activity, and increases collagen production, highlighting the potential of the silica carbonate biomorphs for tissue regeneration. PMID:26455427

  7. Effect of roasting time of buckwheat groats on the formation of Maillard reaction products and antioxidant capacity.

    PubMed

    Małgorzata, Wronkowska; Konrad, Piskuła Mariusz; Zieliński, Henryk

    2016-04-01

    Changes in the formation of Maillard reaction products and antioxidant capacity of buckwheat, induced by roasting at 160 °C for 30, 40 and 50 min, were evaluated in the study. Furozine, was detected after roasting, in all buckwheat samples. Increase of FIC, the presence of significant amounts of CML and enhanced browning were observed, along with increasing times of roasting. The formation of acrylamide in the obtained buckwheat products was also significantly connected with the time of roasting. A significant degradation was observed in natural antioxidants, as affected by heat treatment time. The colour parameter changed significantly with the increasing of roasting time. Overall, 30min of roasting was beneficial from a nutritional point of view for the obtained buckwheat product. PMID:26593501

  8. Asymmetrical ClO3 - Its possible formation from ClO and O2 and its possible reactions

    NASA Technical Reports Server (NTRS)

    Prasad, S. S.; Adams, W. M.

    1980-01-01

    An analysis of recent accurate experimental studies of Cl2-photosensitized O3 decomposition, in which O3 disappearance and OClO formation were directly monitored, suggests the possibility that the suppression of the quantum yield in the presence of O2 may be due to the formation of asymmetrical chlorine trioxide (ClO.O2). Other intermediaries, such as Cl2O2, which may also form in the system are not thought to explain the observations. In addition to its capacity to oxidize, which it shares with other peroxo compounds, asymmetrical ClO3 appears to undergo an interesting class of reactions in which the loosely bound O2 adduct is relatively easily displaced by reactive atoms and radicals such as chlorine.

  9. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  10. Does slow energy transfer limit the observed time constant for radical pair formation in photosystem II reaction centers?

    PubMed

    Rech, T; Durrant, J R; Joseph, D M; Barber, J; Porter, G; Klug, D R

    1994-12-13

    We have used spectrally photoselective femtosecond transient absorption spectroscopy on photosystem II reaction centers to show that there are at least two pools of chlorin molecules/states which can transfer excitation energy to P680, the primary electron donor in photosystem II. It has previously been shown that one chlorin pool equilibrates with P680 in 100 fs [Durrant et al. (1992) Proc. Natl. Acad. Sci. U.S.A. 89, 11632-11636], and we report here the observation of energy transfer from a second more weakly coupled chlorin pool. The effect of the weakly coupled pool is to increase the apparent time constant for radical pair formation from 21 ps when P680 is selectively excited to 27 ps when the accessory chlorins are excited. We conclude that it is possible to observe both radical pair formation somewhat slowed by an energy transfer step and radical pair formation not limited by this slow energy transfer, depending upon which chromophores are initially excited. These observations provide evidence that when using photoselective excitation of P680, the observed 21 ps time constant for radical pair formation is not limited by a slow energy transfer step. PMID:7993905

  11. Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

    NASA Astrophysics Data System (ADS)

    Chambon, J.; Lemming, G.; Manoli, G.; Broholm, M. M.; Bjerg, P.; Binning, P. J.

    2011-12-01

    Enhanced Reductive Dechlorination (ERD) has been successfully used in high permeability media, such as sand aquifers, and is considered to be a promising technology for low permeability settings. Pilot and full-scale applications of ERD at several sites in Denmark have shown that the main challenge is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion transport processes, and this affects the timeframes for the remediation. Due to the limited ERD applications and the complex transport and reactive processes occurring in low-permeability media, design guidelines are currently not available for ERD in such settings, and remediation performance assessments are limited. The objective of this study is to combine existing knowledge from several sites with numerical modeling to assess the effect of the injection interval, development of bioactive zones and reaction kinetics on the remediation efficiency for ERD in diffusion-dominated media. A numerical model is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities and hydraulic parameters, which are relevant for clay till sites in general. The numerical model couples flow and transport in the fracture network and low-permeability matrix. Sequential degradation of TCE to ethene is modeled using Monod kinetics, and the kinetic parameters are obtained from laboratory experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected

  12. Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Clary, D. W.; Gardiner, W. C., Jr.; Stein, S. E.

    1986-01-01

    The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

  13. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    NASA Astrophysics Data System (ADS)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  14. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  15. Acetonitrile and N-Chloroacetamide Formation from the Reaction of Acetaldehyde and Monochloramine.

    PubMed

    Kimura, Susana Y; Vu, Trang Nha; Komaki, Yukako; Plewa, Michael J; Mariñas, Benito J

    2015-08-18

    Nitriles and amides are two classes of nitrogenous disinfection byproducts (DBPs) associated with chloramination that are more cytotoxic and genotoxic than regulated DBPs. Monochloramine reacts with acetaldehyde, a common ozone and free chlorine disinfection byproduct, to form 1-(chloroamino)ethanol. Equilibrium (K1) and forward and reverse rate (k1,k-1) constants for the reaction between initial reactants and 1-(chloroamino)ethanol were determined between 2 and 30 °C. Activation energies for k1 and k-1 were 3.04 and 45.2 kJ·mol(-1), respectively, and enthalpy change for K1 was -42.1 kJ·mol(-1). In parallel reactions, 1-(chloroamino)ethanol (1) slowly dehydrated (k2) to (chloroimino)ethane that further decomposed to acetonitrile and (2) was oxidized (k3) by monochloramine to produce N-chloroacetamide. Both reactions were acid/base catalyzed, and rate constants were characterized at 10, 18, and 25 °C. Modeling for drinking water distribution system conditions showed that N-chloroacetamide and acetonitrile concentrations were 5-9 times higher at pH 9.0 compared to 7.8. Furthermore, acetonitrile concentration was found to form 7-10 times higher than N-chloroacetamide under typical monochloramine and acetaldehyde concentrations. N-chloroacetamide cytotoxicity (LC50 = 1.78 × 10(-3) M) was comparable to dichloroacetamide and trichloroacetamide, but less potent than N,2-dichloroacetamide and chloroacetamide. While N-chloroacetamide was not found to be genotoxic, N,2-dichloroacetamide genotoxic potency (5.19 × 10(-3) M) was on the same order of magnitude as chloroacetamide and trichloroacetamide. PMID:26167888

  16. The Al-Al3Ni Eutectic Reaction: Crystallography and Mechanism of Formation

    NASA Astrophysics Data System (ADS)

    Fan, Yangyang; Makhlouf, Makhlouf M.

    2015-09-01

    The characteristics of the Al-Al3Ni eutectic structure are examined with emphasis on its morphology and crystallography. Based on these examinations, the mechanism of formation of this technologically important eutectic is postulated. It is found that a thin shell of α-Al forms coherently around each Al3Ni fiber. The excellent thermal stability of the Al-Al3Ni eutectic may be attributed to the presence of this coherent layer.

  17. Synthetic studies toward halichlorine: complex azaspirocycle formation with use of an NBS-promoted semipinacol reaction.

    PubMed

    Hurley, Paul B; Dake, Gregory R

    2008-06-01

    The investigations of a synthetic route incorporating a NBS-promoted semipinacol rearrangement to the 6-azaspiro[4.5]decane fragment within halichlorine ( 1) are presented. A convergent approach was pursued, utilizing two chiral, enantiomerically enriched building blocks, 2-trimethylstannyl piperidene 10 and substituted cyclobutanone 19. Noteworthy synthetic operations in this study include the following: (a) a highly diastereoselective NBS-promoted semipinacol reaction that established four stereogenic centers in ketone 25 and (b) the use of a N- p-toluenesulfonyl-2-iodo-2-piperidene as a precursor to a basic organometallic reagent, which was critical to the success of the coupling of fragments 10 and 19. PMID:18444680

  18. Formation of water soluble complexes of ?: solid-state reaction between tertiary amines and ?

    NASA Astrophysics Data System (ADS)

    Mohan, H.; Priyadarsini, K. I.; Tyagi, A. K.; Mittal, J. P.

    1996-11-01

    Water soluble complexes of 0953-4075/29/21/015/img3 have been prepared on solid-state mechano-chemical reaction between 0953-4075/29/21/015/img3 and tertiary amines (hexamine, DABCO) at room temperature 0953-4075/29/21/015/img5. The product is characterized by x-ray diffraction and FTIR methods. It is presumably due to the charge transfer interactions between electron affinic 0953-4075/29/21/015/img3 and electron rich tertiary amines.

  19. Green's Function Reaction Dynamics—An Exact and Efficient Way To simulate Intracellular Pattern Formation

    NASA Astrophysics Data System (ADS)

    Sokolowski, Thomas; Bossen, Laurens; Miedema, Thomas; Becker, Nils

    2010-09-01

    Active transport of intracellular cargo on cytoskeletal polymers via ATP-driven motor proteins plays a key role in establishing well-defined spatial patterns of functional intracellular components, which can range from proteins to big organelles like mitochondria. It is the interplay between active transport, diffusive movement in the cytosol and the geometry of the cell and its cytoskeleton that finally determines the distribution of the transported objects. To analyze such phenomena we extend our Green's Function Reaction Dynamics (GFRD) framework to allow for an exact event-driven simulation of active transport on microtubules and interactions with the cell membrane.

  20. Antioxidants Inhibit Formation of 3-Monochloropropane-1,2-diol Esters in Model Reactions.

    PubMed

    Li, Chang; Jia, Hanbing; Shen, Mingyue; Wang, Yuting; Nie, Shaoping; Chen, Yi; Zhou, Yongqiang; Wang, Yuanxing; Xie, Mingyong

    2015-11-11

    The capacities of six antioxidants to inhibit the formation of 3-monochloropropane-1,2 diol (3-MCPD) esters were examined in this study. Inhibitory capacities of the antioxidants were investigated both in chemical models containing the precursors (tripalmitoyl glycerol, 1,2-dipalmitoyl-sn-glycerol, monopalmitoyl glycerol, and sodium chloride) of 3-MCPD esters and in oil models (rapeseed oil and sodium chloride). Six antioxidants, butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), L-ascorbyl palmitate (AP), and α-tocopherol (VE), were found to exhibit inhibiting capacities on 3-MCPD ester formation both in chemical models and in oil models. TBHQ provided the highest inhibitory capacity both in chemical models and in oil models; 44% of 3-MCPD ester formation was inhibited in the presence of TBHQ (66 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min, followed by PG and AP. BHT, BHA, and VE appeared to have weaker inhibitory abilities in both models. VE exhibited the lowest inhibition rate; 22% of 3-MCPD esters were inhibited in the presence of VE (172 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min. In addition, the inhibition rates of PG and VE decreased dramatically with an increase in temperature or heating time. The results suggested that some antioxidants, such as TBHQ, PG, and AP, could be the potential inhibitors of 3-MCPD esters in practice. PMID:26478126

  1. Geochronology and geochemistry of a dyke host rock association and implications for the formation of the Bavarian Pfahl shear zone, Bohemian Massif

    NASA Astrophysics Data System (ADS)

    Siebel, Wolfgang; Blaha, Ulrich; Chen, Fukun; Rohrmüller, Johann

    2005-02-01

    To place constraints on the formation and deformation history of the major Variscan shear zone in the Bavarian Forest, Bavarian Pfahl zone, SW Bohemian Massif, granitic dykes and their feldspar-phyric massive host rock (so-called “palite”), zircons were dated by the U Pb isotope dilution and Pb-evaporation methods. The dated samples comprise two host rocks and four dykes from a K-rich calc-alkaline complex adjoining the SW part of the Bavarian Pfahl shear zone. The palites, which appear to be the oldest magmatic rocks emplaced in the shear zone, yield ages of 334±3, 334.5±1.1 Ma (average 207Pb/206Pb-evaporation zircon ages) and 327 342 Ma (range of U/Pb zircon ages) suggesting a Lower Carboniferous age for the initiation of the Pfahl zone. Absence of inherited older cores in all investigated zircons indicates that incorporation of crustal zircon material has played virtually no role or that the melting temperature was very high. Determination of the dyke emplacement age is complicated by partial Pb-loss in most of the fractions analysed. This Pb-loss can be ascribed to higher U content of the dyke zircons compared to those from host rock. Upper discordia intercept ages of the different dykes range from 322±5 to 331±9 Ma. The dykes are pre- to synkinematic with respect to penetrative regional mylonitisation along the Pfahl zone, and the upper intercept ages provide a maximum age for this tectonic event.

  2. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    SciTech Connect

    Vohra, Manav; Winokur, Justin; Overdeep, Kyle R.; Marcello, Paul; Weihs, Timothy P.; Knio, Omar M.

    2014-12-21

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  3. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products.

    PubMed

    Ji, Yuefei; Kong, Deyang; Lu, Junhe; Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo

    2016-08-01

    Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO4(-)) with TBBPA was determined to be 5.27×10(10)M(-1)s(-1). Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO4(-). Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6-10h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health. PMID:27107323

  4. Secondary Organic Aerosol Formation by Cloud Processing: Accretion Reactions Involving Glyoxal and Methylglyoxal in Evaporating Cloud Droplets

    NASA Astrophysics Data System (ADS)

    de Haan, D. O.; Hastings, W. P.; Corrigan, A. L.; Lee, F. E.; Hanley, S. W.

    2006-12-01

    Glyoxal and methyl glyoxal are dicarbonyl compounds found in atmospheric cloud and fog water, typically at low micromolar concentrations. These two compounds are known to form copolymers under certain industrial conditions by the nucleophilic addition of S, N and O-containing molecules. We report ambient FTIR-ATR and particle chamber data on a range of reactions between glyoxal and S, N and O-containing molecules found in cloudwater, some of which are triggered by droplet evaporation. Liquid-phase formation of adducts between glyoxal and S(IV) is seen to halt sulfur oxidation during droplet drying on the ATR crystal. Formation of glyoxal / S(VI) adducts, however, are not observed by ATR. At neutral or acidic pH, droplet evaporation triggers a reaction between glyoxal and amino acids in the residue left behind, forming imines. Glyoxal reacts under similar conditions with glycol compounds, forming cyclic acetals, but not with sugars, perhaps due to a lack of conformational freedom. Glyoxal is not observed to react with carboxylic acids, either in particle chambers or while drying on an ATR crystal.

  5. The dynamics of serpentinite dehydration reactions in subduction zones: Constrains from the Cerro del Almirez ultramafic massif (Betic Cordillera, SE Spain)

    NASA Astrophysics Data System (ADS)

    Dilissen, Nicole; Garrido, Carlos J.; López Sánchez-Vizcaíno, Vicente; Padrón-Navarta, José Alberto

    2015-04-01

    Arc volcanism, earthquakes and subduction dynamics are controlled by fluids from downgoing slabs and their effect on the melting and rheology of the overlying mantle wedge. High pressure dehydration of serpentinite in the slab and the subduction channel is considered as one of the main sources of fluids in subduction zones. Even though this metamorphic reaction is essential in subduction activities, the behavior of the fluids, the kinetics and thermodynamics during the breakdown reaction are still poorly understood. The Cerro del Almirez (Nevado-Filábride Complex, Betic Cordillera, SE Spain) uniquely preserves the dehydration front from antigorite serpentinite to chlorite-harzburgite and constitutes a unique natural laboratory to investigate high-pressure dehydration of serpentinite. This reaction occurred in a subduction setting releasing up to 13 wt% of water, contributing significantly to the supply of fluids to the overlying mantle wedge. A key to the understanding of the metamorphic conditions prevailing during serpentinite dehydration is to study the two prominent textures -granofels and spinifex-like chlorite harzburgite- occurring in this reaction product. The detailed texture differences in the Chl-harzburgite can provide insights into diverse kinetic and thermodynamic conditions of this dehydration reaction due to variations in effective pressure and drainage conditions. It has been proposed that difference in overpressure (P') and deviation from growth equilibrium, i.e. overstepping, is responsible for these two types of textures [Padrón-Navarta et al., 2011]. The magnitude and duration of P' is highly dependent on dehydration kinetics [Connolly, 1997]. The fast pressure drop, with spinifex-texture as a product, can be linked to draining events expected after hydrofracturing, which are recorded in grain size reduction zones in this massif. According to this hypothesis, mapping of textural variation in Chl-harzburgite might be used as a proxy to

  6. Reactions of OOH radical with beta-carotene, lycopene, and torulene: hydrogen atom transfer and adduct formation mechanisms.

    PubMed

    Galano, Annia; Francisco-Marquez, Misaela

    2009-08-13

    The relative free radical scavenging activity of beta-carotene, lycopene, and torulene toward OOH radicals has been studied using density functional theory. Hydrogen atom transfer (HAT) and radical adduct formation (RAF) mechanisms have been considered. All the possible reaction sites have been included in the modeling, and detailed branching ratios are reported for the first time. The reactions of hydrocarbon carotenoids (Car) with peroxyl radicals, in both polar and nonpolar environments, are predicted to proceed via RAF mechanism, with contributions higher than 98% to the overall OOH + Car reactions. Lycopene and torulene were found to be more reactive than beta-carotene. In nonpolar environments the reactivity of the studied carotenoids toward peroxyl radical follows the trend LYC > TOR > BC, whereas in aqueous solutions it is TOR > LYC > BC. OOH adducts are predicted to be formed mainly at the terminal sites of the conjugated polyene chains. The main addition sites were found to be C5 for beta-carotene and lycopene and C30 for torulene. The general agreement between the calculated magnitudes and the available experimental data supports the predictions from this work. PMID:19627101

  7. Ammonia formation from NO reaction with surface hydroxyls on rutile TiO2 (110) - 1×1

    SciTech Connect

    Kim, Boseong; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2015-01-15

    The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formed in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .

  8. Unexpected formation of π-expanded isoquinoline from anthracene possessing four electron-donating groups via the Duff reaction.

    PubMed

    Węcławski, Marek K; Deperasińska, Irena; Leniak, Arkadiusz; Banasiewicz, Marzena; Kozankiewicz, Bolesław; Gryko, Daniel T

    2016-08-01

    New synthetic methods leading towards π-expanded heterocycles are sought after mainly due to their promising opto-electronic properties. Subjecting 1,5,9,10-tetramethoxyanthracene to the modern Duff reaction conditions led to the formation of a compound possessing the 2-azabenzoanthrone (dibenzo[de,h]isoquinolin-7-on) skeleton instead of the expected dialdehyde. This non-typical course of reaction can be rationalized by the double electrophilic aromatic substitution at two neighboring electron-rich positions of anthracene followed by oxidation of the resulting intermediate to form a pyridine ring. Optical studies supported by the quantum chemistry calculations indicated the lack of excited-state intramolecular proton transfer (ESIPT); for energy reasons, only one tautomeric form, with a hydrogen atom bonded to one of the two nearby oxygen atoms, was populated in the electronic ground S0 and in the excited S1 states. Nonradiative depopulation of the S1 state proceeded via internal conversion stimulated by the presence of the low frequency vibrational modes. Our serendipitous discovery represents the most complex case of rearrangement of aromatic compounds under Duff reaction conditions and could help to design analogous processes. At the same time this is the simplest method for the synthesis of derivatives of 2-azabenzoanthrone. PMID:27367169

  9. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    PubMed

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  10. Case with Brunsting-Perry-like localized subepidermal blister formations and immunoglobulin G antibodies against unidentified basement membrane zone antigen.

    PubMed

    Sato-Shibuya, Mami; Dainichi, Teruki; Egawa, Gyohei; Honda, Tetsuya; Otsuka, Atsushi; Ishii, Norito; Hashimoto, Takashi; Miyachi, Yoshiki; Kabashima, Kenji

    2016-04-01

    Brunsting-Perry type bullous pemphigoid is defined by the blister formation limited to the head and neck, and autoantibodies to type VII collagen are detected in several cases. However, the pathomechanisms and autoantigens in this condition remain unknown. We report a 20-year-old female patient with a more than 2-year history of recurrent tense blisters localized on the face with no distinct atrophic scar formation. The patient had neither extensive sun exposure nor a history suggestive of contact dermatitis. Oral betamethasone was effective on the skin lesions. Histopathology revealed subepidermal blister formation with dermal infiltrates of neutrophils. Although direct and indirect immunofluorescence tests detected immunoglobulin G antibodies to the basement membrane zone (BMZ), no known dermal or epidermal autoantigens were detected in immunoblot analyses. Therefore, this case may be a rare variant of Brunsting-Perry type localized bullous pemphigoid with autoantibodies to an undetermined BMZ antigen. PMID:26362108

  11. Reactions Between Water Soluble Organic Acids and Nitrates in Atmospheric Aerosols: Recycling of Nitric Acid and Formation of Organic Salts

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander

    2014-03-25

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate Ca(NO3)2 when nitrogen oxide and nitric acid (HNO3) species react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here, we present a systematic microanalysis study on chemical composition of laboratory generated particles composed of water soluble organic acids and nitrates (i.e. NaNO3 and Ca(NO3)2) investigated using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and Fourier transform infrared micro-spectroscopy (micro-FTIR). The results show that water-soluble organic acids can react with nitrates releasing gaseous HNO3 during dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase due to its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that in turn may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling, which may further affect concentrations of gas- and aerosol-phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  12. Formation of biphenyl and dibenzofuran phytoalexins in the transition zones of fire blight-infected stems of Malus domestica cv. 'Holsteiner Cox' and Pyrus communis cv. 'Conference'.

    PubMed

    Chizzali, Cornelia; Khalil, Mohammed N A; Beuerle, Till; Schuehly, Wolfgang; Richter, Klaus; Flachowsky, Henryk; Peil, Andreas; Hanke, Magda-Viola; Liu, Benye; Beerhues, Ludger

    2012-05-01

    In the rosaceous subtribe Pyrinae (formerly subfamily Maloideae), pathogen attack leads to formation of biphenyls and dibenzofurans. Accumulation of these phytoalexins was studied in greenhouse-grown grafted shoots of Malus domestica cv. 'Holsteiner Cox' and Pyrus communis cv. 'Conference' after inoculation with the fire blight bacterium, Erwinia amylovora. No phytoalexins were found in leaves. However, both classes of defence compounds were detected in the transition zone of stems. The flanking stem segments above and below this zone, which were necrotic and healthy, respectively, were devoid of detectable phytoalexins. The transition zone of apple stems contained the biphenyls 3-hydroxy-5-methoxyaucuparin, aucuparin, noraucuparin and 2'-hydroxyaucuparin and the dibenzofurans eriobofuran and noreriobofuran. In pear, aucuparin, 2'-hydroxyaucuparin, noreriobofuran and in addition 3,4,5-trimethoxybiphenyl were detected. The total phytoalexin content in the transition zone of pear was 25 times lower than that in apple. Leaves and stems of mock-inoculated apple and pear shoots lacked phytoalexins. A number of biphenyls and dibenzofurans were tested for their in vitro antibacterial activity against some Erwinia amylovora strains. The most efficient compound was 3,5-dihydroxybiphenyl (MIC=115 μg/ml), the immediate product of biphenyl synthase which initiates phytoalexin biosynthesis. PMID:22377689

  13. Thermal evolution of the Sisters shear zone, southern New Zealand; Formation of the Great South Basin and onset of Pacific-Antarctic spreading

    NASA Astrophysics Data System (ADS)

    Kula, Joseph; Tulloch, Andy J.; Spell, Terry L.; Wells, Michael L.; Zanetti, Kathleen A.

    2009-10-01

    The separation of Zealandia from West Antarctica was the final stage in the Cretaceous breakup of the Gondwana Pacific margin. Continental extension resulting in formation of the Great South Basin and thinning of the Campbell Plateau leading to development of the Pacific-Antarctic spreading ridge was partially accommodated along the Sisters shear zone. This east-northeast striking brittle-ductile structure exposed along the southeast coast of Stewart Island, New Zealand, is a greenschist facies extensional shear zone that separates a hanging wall of chloritic, brecciated granites, and undeformed conglomerate from a footwall of mylonitic Carboniferous and Early Cretaceous granites. This complex structure exhibits bivergent kinematics and can be subdivided into a northern and southern segment. The 40Ar/39Ar thermochronology indicates that cooling of the shear zone footwall began at ˜94 Ma with accelerated cooling over the interval ˜89-82 Ma. Structural and thermochronological data indicate a spatial and temporal link between the Sisters shear zone, initial sedimentation within the offshore Great South Basin, extension of the Campbell Plateau, and initiation of the Pacific-Antarctic spreading ridge.

  14. Formation of hyperdeformed states in capture reactions at sub-barrier energies

    SciTech Connect

    Zubov, A. S.; Antonenko, N. V.; Sargsyan, V. V.; Adamian, G. G.; Scheid, W.

    2010-09-15

    The high-spin hyperdeformed nuclear states treated as dinuclear or quasimolecular configurations are suggested to be directly populated in heavy ion collisions at sub-barrier energies. Tunneling through the Coulomb barrier is considered using the quantum diffusion approach based on the formalism of reduced density matrix. The reactions {sup 48}Ca+{sup 86}Kr,{sup 124}Sn,{sup 136}Xe,{sup 138}Ba,{sup 140}Ce, {sup 58}Ni+{sup 58}Ni, and {sup 40,48}Ca+{sup 40,48}Ca, are suggested for populating high-spin hyperdeformed states. The partial production and identification cross sections for the hyperdeformed states are calculated as the functions of bombarding energy.

  15. Iron disilicide formation by Au-Si eutectic reaction on Si substrate

    NASA Astrophysics Data System (ADS)

    Akiyama, Kensuke; Kaneko, Satoru; Yokomizo, Kazuya; Itakura, Masaru

    2009-11-01

    We have investigated the growth of iron disilicide on Au-coated Si(0 0 1) substrates and its photoluminescence behaviour. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy observations revealed that the Si surface above 380 °C was melted as a result of the Au-Si eutectic reaction and that coarse island disilicide grains with sizes of several micrometres were formed on the Si surface. The full width at half maximum of 0.056° on the rocking curve of α-FeSi 2004 was observed on the sample deposited at 800 °C, and indicated the high crystal quality in perfection of orientation. The photoluminescence spectrum of β-FeSi 2 grains, which were deposited at 750 °C, was observed. The melted Si surface contributed to the improved crystallinity of α-FeSi 2 and β-FeSi 2.

  16. The effect of reaction conditions on formation of wet precipitated calcium phosphates

    NASA Astrophysics Data System (ADS)

    Huang, Chen; Cao, Peng

    2015-03-01

    The precipitation process discussed in the present study involves the addition of alkaline solutions to an acidic calcium phosphate suspension. Several parameters (pH, pH buffer reagent, ageing and stirring) were investigated. The synthesized powders were calcined at 1000°C for 1 h in air, in order to study the thermal stability and crystalline phase compositions. X-ray diffraction (XRD) and ESEM analysis were used for sample characterization. It is found that all these processing parameters affect the crystalline phases evolved and resultant microstructures. Phase evolution occurred at an elevated pH level. The pH buffer reagent would affect both the phase composition and microstructure. Ageing was essential for the phase maturation. Stirring accelerated the reaction process by providing a homogeneous medium for precipitation.

  17. Photo-induced hydrogen exchange reaction between methanol and glyoxal: formation of hydroxyketene.

    PubMed

    Mielke, Zofia; Mucha, Małgorzata; Bil, Andrzej; Golec, Barbara; Coussan, Stephane; Roubin, Pascale

    2008-08-25

    We study the structure and photochemistry of the glyoxal-methanol system (G-MeOH) by means of FTIR matrix isolation spectroscopy and ab initio calculations. The FTIR spectra show that the non-hydrogen-bonded complex, G-MeOH-1, is present in an inert environment of solid argon. MP2/aug-cc-pVDZ calculations indicate that G-MeOH-1 is the most stable complex among the five optimized structures. The interaction energy partitioned according to the symmetry-adapted perturbation theory (SAPT) scheme demonstrates that the dispersion energy gives a larger contribution to the stabilization of a non-hydrogen-bonded G-MeOH-1 complex than compared to the hydrogen-bonded ones. The irradiation of G-MeOH-1 with the filtered output of a mercury lamp (lambda>370 nm) leads to its photo-conversion into the hydroxyketene-methanol complex HK-MeOH-1. The identity of HK-MeOH-1 is confirmed by both FTIR spectroscopy and MP2/aug-cc-pVDZ calculations. An experiment with deuterated methanol (CH(3)OD) evidences that hydroxyketene is formed in a photo-induced hydrogen exchange reaction between glyoxal and methanol. The pathway for the photo-conversion of G-MeOH-1 to HK-MeOH-1 is studied by a coupled-cluster method [CR-CC(2,3)]. The calculations confirm our experimental findings that the reaction proceeds via hydrogen atom exchange between the OH group of methanol and CH group of glyoxal. PMID:18613199

  18. Magma formation in hot-slab subduction zones: Insights from hydrogen isotopes in Cascade Arc melt inclusions

    NASA Astrophysics Data System (ADS)

    Walowski, K. J.; Wallace, P. J.; Hauri, E. H.; Clynne, M. A.; Rea, J.; Rasmussen, D. J.

    2013-12-01

    In a comparison of arcs globally, primitive basaltic magmas in the Cascades have slightly lower H2O concentrations, consistent with the hotter nature of the young subducted plate [Ruscitto et al., 2012]. In addition, geodynamic models [Syracuse et al., 2010] and geochemical studies [Cooper et al., 2012] agree that slab surface temperatures beneath the Cascade arc axis are hotter, on average, than in many other arcs. Data on volatiles and their relationships to fluid mobile trace elements are key to understanding volatile recycling and the formation of arc magmas. Here, we present the first data on hydrogen isotopes (D/H) in basaltic melt inclusions (MI) from the Cascades, as measured by NanoSIMS, in conjunction with a complete dataset on volatile, major, and trace elements in the MI. Recent work on MI from the Marianas [Shaw et al., 2012] has shown the potential for using δD to understand the cycling of hydrous fluids through subduction zones. Our samples were collected from cinder cones in the Lassen region of the southern Cascades (6 calc-alkaline basalts [CAB] and 2 transitional between CAB and low-K tholeiite [LKT]), and 2 basaltic tephra units from Mount St. Helens (MSH) that have OIB-like trace element characteristics, which is common in the central part of the arc. Using the maximum volatile contents at each cone to represent the undegassed magma, we find values of 2.1-3.4 wt% H2O and 500-1200 ppm CO2 for CABs and 1.15-1.30 wt% H2O and 750-850 ppm CO2 for transitional LKTs (all corrected to be in eq. with Fo90 olivine) in the Lassen Region. At MSH, we find 1.7 wt% H2O and <300 ppm CO2 for the OIB samples. For CABs from the Lassen Region, (Sr/P)N correlates with slab fluid tracers such as H2O/Ce and Cl/Nb, indicating a link between volatile and trace element enrichment of the mantle wedge, but transitional LKTs deviate slightly from the overall pattern. At MSH, values of (Sr/P)N, H2O/Ce, and Cl/Nb are lower than those in the Lassen Region, and are more

  19. Flavor of oranges as impacted by abscission zone formation for trees affected by huanglongbing disease and Lasiodiploida infection

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Trees affected by Huanglongbing (HLB) exhibit excessive fruit drop, which is exacerbated by secondary infection of the abscission zone by the fungus Lasiodiplodia. ‘Hamlin’ orange trees, both healthy and affected by HLB, Candidatus Liberibacter asiaticus (CLas, determined by Polymerase chain reactio...

  20. Dynamics of intraoceanic subduction initiation: 1. Oceanic detachment fault inversion and the formation of supra-subduction zone ophiolites

    NASA Astrophysics Data System (ADS)

    Maffione, Marco; Thieulot, Cedric; van Hinsbergen, Douwe J. J.; Morris, Antony; Plümper, Oliver; Spakman, Wim

    2015-06-01

    Subduction initiation is a critical link in the plate tectonic cycle. Intraoceanic subduction zones can form along transform faults and fracture zones, but how subduction nucleates parallel to mid-ocean ridges, as in e.g., the Neotethys Ocean during the Jurassic, remains a matter of debate. In recent years, extensional detachment faults have been widely documented adjacent to slow-spreading and ultraslow-spreading ridges where they cut across the oceanic lithosphere. These structures are extremely weak due to widespread occurrence of serpentine and talc resulting from hydrothermal alteration, and can therefore effectively localize deformation. Here, we show geochemical, tectonic, and paleomagnetic evidence from the Jurassic ophiolites of Albania and Greece for a subduction zone formed in the western Neotethys parallel to a spreading ridge along an oceanic detachment fault. With 2-D numerical modeling exploring the evolution of a detachment-ridge system experiencing compression, we show that serpentinized detachments are always weaker than spreading ridges. We conclude that, owing to their extreme weakness, oceanic detachments can effectively localize deformation under perpendicular far-field forcing, providing ideal conditions to nucleate new subduction zones parallel and close to (or at) spreading ridges. Direct implication of this, is that resumed magmatic activity in the forearc during subduction initiation can yield widespread accretion of suprasubduction zone ophiolites at or close to the paleoridge. Our new model casts the enigmatic origin of regionally extensive ophiolite belts in a novel geodynamic context, and calls for future research on three-dimensional modeling of subduction initiation and how upper plate extension is associated with that.

  1. Formation of tungsten carbide nanoparticles on graphitized carbon to facilitate the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; He, Guoqiang; Cai, Mei; Meng, Hui; Shen, Pei Kang

    2013-11-01

    Tungsten carbide nanoparticles with the average size less than 5 nm uniformly dispersed on the graphitized carbon matrix have been successfully synthesized by a one-step ion-exchange method. This route is to locally anchor the interested species based on an ionic level exchange process using ion-exchange resin. The advantage of this method is the size control of targeted nanomaterial as well as the graphitization of resin at low temperatures catalyzed by iron salt. The Pt nanoparticles coupled with tungsten carbide nanoparticles on graphitized carbon nanoarchitecture form a stable electrocatalyst (Pt/WC-GC). The typical Pt/WC-GC electrocatalyst gives a Pt-mass activity of 247.7 mA mgPt-1, which is much higher than that of commercial Pt/C electrocatalyst (107.1 mA mgPt-1) for oxygen reduction reaction due to the synergistic effect between Pt and WC. The presented method is simple and could be readily scaled up for mass production of the nanomaterials.

  2. A simulation and time series analysis of reaction- diffusion equations in biological pattern formation

    NASA Astrophysics Data System (ADS)

    Cooper, Crystal Diane

    A computer program was modified to model the dynamics of morphogen concentrations in a developing eye of a Xenopus laevis frog. The dynamics were modelled because it is believed that the behavior of the morphogen concentrations determine how the developing eye maps to the brain. The eye in the xenophus grows as a series of rings, and thus this is the model used. The basis for the simulation are experiments done by Sullivan et al. Following the experiment, aIl eye ring is 'split' in half, inverted, and then 'pasted' onto a donor half. The purpose of the program is to replicate and analyze the results that were found experimentally: a graft made on a north to south axis (dorsal to ventral) produces a change in vision along the east to west axis (anterior to posterior). Four modified Gierer-Meinhardt reaction- diffusion equations are used to simulate the operation. In the second part of the research, the program was further modified and a time series analysis was done on the results. It was found that the modified Gierer- Meinhardt equations demonstrated chaotic behavior under certain conditions. The dynamics included fixed points, limit cycles, transient chaos, intermittent chaos, and strange attractors. The creation and destruction of fractal torii was found.

  3. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol a-linkages in lignin: a density functional theory study

    SciTech Connect

    Watts, Heath D.; Mohamed, Mohamed Naseer Ali; Kubicki, James D.

    2011-01-01

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  4. A new mechanism of loop formation and transformation in bcc iron without dislocation reaction

    NASA Astrophysics Data System (ADS)

    Chen, J.; Gao, N.; Jung, P.; Sauvage, T.

    2013-10-01

    Structure and kinetics of dislocation loops in α-Fe is an active field in material science, due to their implications on fundamental understanding as well as application of structural materials in irradiation environments. Recent computer simulations provoke new conceptions, which call for experimental verification. The present investigation reports transmission electron microscopy of small interstitial dislocation loops (2.5-10 nm diameters) in bcc iron, irradiated with 25 MeV α-particles at 573 K up to 0.13 dpa. The observed <1 0 0> and ½<1 1 1> loops have habit planes of (1 0 0), and (1 1 0), (1 1 1) and (2 1 1), respectively. Furthermore it is observed that loops also contain ½<1 1 1>{2 1 1} and <1 0 0>{1 0 0} components which are considered as intermediate stages of transformation of ½<1 1 1> loops to <1 0 0>. Based on these observations, a new mechanism of loop formation and transformation by self-interstitial atoms aggregation is proposed, with concurrent molecular dynamic simulations supporting the kinetic feasibility of the proposed process.

  5. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2

    NASA Astrophysics Data System (ADS)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B.

    2016-05-01

    The anilide anion ( m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion ( m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion ( m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  6. Particle formation and characterization of mackerel reaction oil by gas saturated solution process.

    PubMed

    Tanbirul Haque, A S M; Chun, Byung-Soo

    2016-01-01

    Most of the health benefits of fish oil can be attributed to the presence of omega-3 fatty acids like Docosahexenoic acid (DHA) and Eicosapentaenoic acid (EPA). There are few dietary sources of EPA and DHA other than oily fish. EPA and DHA have great potential effect on human health. In this research, Supercritical carbon dioxide (scCO2) extracted mackerel oil was reacted by enzyme at different systems to improve the EPA and DHA. Different types of immobilize enzyme TL-IM, RM-IM, Novozyme 435 were assessed for improving PUFAs. Best result was found at non-pressurized system using TL-IM. Reacted oil particle were obtained with polyethylene glycol by gas saturated solution process (PGSS). Different parameters like temperature, pressure, agitation speed and nozzle size effect on particle formulation were observed. SEM and PSA analysis showed, small size non spherical particles were obtained. It was found that after particle formation poly unsaturated fatty acids (PUFAs) were present in particle as same in oil. PUFAs release from particle was almost linear against constant time duration. Oil quality in particle not change significantly, in this contrast this study will be helpful for food and pharmaceutical industry to provide high EPA and DHA containing powder. PMID:26787949

  7. Formation of semiconductor Cu{sub 2-x}Se rod-like crystals through a solvothermal reaction

    SciTech Connect

    Liu Yuanfang; Zeng Jinghui; Li Cun; Cao Jinbo; Wang Yuanyuan; Qian Yitai

    2002-12-01

    Micron-sized rod-like crystals of Cu{sub 2-x}Se were successfully grown for the first time by a hydrothermal reaction from CuCl{sub 2}{center_dot}2H{sub 2}O and Se powder at 60 deg. C for 2 h. X-ray powder diffraction patterns (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM) images, and transmission electron microscope (TEM) images show that the product is cubic Cu{sub 2-x}Se rod-like crystal and well crystallized. Hydrazine hydrate was used as solvent in the process and played an important role in the formation of rod-like Cu{sub 2-x}Se crystals. The optical properties of Cu{sub 2-x}Se, such as absorption spectra, photoluminescence (PL) spectra, and Raman spectrum are also reported for the first time.

  8. A coumarin-specific prenyltransferase catalyzes the crucial biosynthetic reaction for furanocoumarin formation in parsley.

    PubMed

    Karamat, Fazeelat; Olry, Alexandre; Munakata, Ryosuke; Koeduka, Takao; Sugiyama, Akifumi; Paris, Cedric; Hehn, Alain; Bourgaud, Frédéric; Yazaki, Kazufumi

    2014-02-01

    Furanocoumarins constitute a sub-family of coumarin compounds with important defense properties against pathogens and insects, as well as allelopathic functions in plants. Furanocoumarins are divided into two sub-groups according to the alignment of the furan ring with the lactone structure: linear psoralen and angular angelicin derivatives. Determination of furanocoumarin type is based on the prenylation position of the common precursor of all furanocoumarins, umbelliferone, at C6 or C8, which gives rise to the psoralen or angelicin derivatives, respectively. Here, we identified a membrane-bound prenyltransferase PcPT from parsley (Petroselinum crispum), and characterized the properties of the gene product. PcPT expression in various parsley tissues is increased by UV irradiation, with a concomitant increase in furanocoumarin production. This enzyme has strict substrate specificity towards umbelliferone and dimethylallyl diphosphate, and a strong preference for the C6 position of the prenylated product (demethylsuberosin), leading to linear furanocoumarins. The C8-prenylated derivative (osthenol) is also formed, but to a much lesser extent. The PcPT protein is targeted to the plastids in planta. Introduction of this PcPT into the coumarin-producing plant Ruta graveolens showed increased consumption of endogenous umbelliferone. Expression of PcPT and a 4-coumaroyl CoA 2'-hydroxylase gene in Nicotiana benthamiana, which does not produce furanocoumarins, resulted in formation of demethylsuberosin, indicating that furanocoumarin production may be reconstructed by a metabolic engineering approach. The results demonstrate that a single prenyltransferase, such as PcPT, opens the pathway to linear furanocoumarins in parsley, but may also catalyze the synthesis of osthenol, the first intermediate committed to the angular furanocoumarin pathway, in other plants. PMID:24354545

  9. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

    PubMed

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B

    2016-05-01

    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions. Graphical Abstract ᅟ. PMID:26914232

  10. Colloid formation and metal transport through two mixing zones affected by acid mine drainage near Silverton, Colorado

    USGS Publications Warehouse

    Schemel, L.E.; Kimball, B.A.; Bencala, K.E.

    2000-01-01

    Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (< 10%) of colloidal Al, Fe and Zn from the water column.

  11. Transformation of ranitidine during water chlorination and ozonation: Moiety-specific reaction kinetics and elimination efficiency of NDMA formation potential.

    PubMed

    Jeon, Dahee; Kim, Jisoo; Shin, Jaedon; Hidayat, Zahra Ramadhany; Na, Soyoung; Lee, Yunho

    2016-11-15

    Ranitidine can produce high yields of N-nitrosodimethylamine (NDMA) upon chloramination and its presence in water resources is a concern for water utilities using chloramine disinfection. This study assessed the efficiency of water chlorination and ozonation in transforming ranitidine and eliminating its NDMA formation potential (NDMA-FP) by determining moiety-specific reaction kinetics, stoichiometric factors, and elimination levels in real water matrices. Despite the fact that chlorine reacts rapidly with the acetamidine and thioether moieties of ranitidine (k>10(8)M(-1)s(-1) at pH 7), the NDMA-FP decreases significantly only when chlorine reacts with the less reactive tertiary amine (k=3×10(3)M(-1)s(-1) at pH 7) or furan moiety (k=81M(-1)s(-1) at pH 7). Ozone reacts rapidly with all four moieties of ranitidine (k=1.5×10(5)-1.6×10(6)M(-1)s(-1) at pH 7) and its reaction with the tertiary amine or furan moiety leads to complete elimination of the NDMA-FP. Treatments of ranitidine-spiked real water samples have shown that ozonation can efficiently deactivate ranitidine in water and wastewater treatment, while chlorination can be efficient for water containing low concentration of ammonia. This result can be applied to the other structurally similar, potent NDMA precursors. PMID:27381234

  12. Growth, reaction and nanowire formation of Fe on the ZnS(1 0 0) surface.

    PubMed

    Man, Ka Lun; Pavlovska, Anastassia; Bauer, Ernst; Locatelli, Andrea; Menteş, Tevfik O; Niño, Miguel A; Wong, George K L; Sou, Iam Keong; Altman, Michael S

    2014-08-01

    The growth and reaction of Fe on a ZnS(1 0 0) substrate are studied in situ and with high lateral resolution using low energy electron microscopy (LEEM), micro low energy electron diffraction ( μLEED), x-ray photoemission electron microscopy (XPEEM), microprobe x-ray photoelectron spectroscopy ( μXPS) and x-ray magnetic circular dichroism PEEM (XMCDPEEM) for complementary structural, chemical, and magnetic characterization. Initially, a two-dimensional (Fe, Zn)S reaction layer forms with thickness that depends on growth temperature. Further growth results in the formation of a variety of three-dimensional crystals, most of them strongly elongated in the form of 'nanowires' of two distinct types, labeled as A and B. Type A nanowires are oriented near the ZnS[1 1 0] direction and are composed of Fe. Type B nanowires are oriented predominantly along directions a few degrees off the ZnS[0 0 1] direction and are identified as Greigite (Fe3S4). Both types of nanowires are magnetic with Curie temperatures above 450 °C. The understanding of the reactive growth mechanism in this system that is provided by these investigations may help to develop growth methods for other elemental and transition metal chalcogenide nanostructures on ZnS and possibly on other II-VI semiconductor surfaces. PMID:24934101

  13. Growth, reaction and nanowire formation of Fe on the ZnS(1 0 0) surface

    NASA Astrophysics Data System (ADS)

    Lun Man, Ka; Pavlovska, Anastassia; Bauer, Ernst; Locatelli, Andrea; Menteş, Tevfik O.; Niño, Miguel A.; Wong, George K. L.; Keong Sou, Iam; Altman, Michael S.

    2014-08-01

    The growth and reaction of Fe on a ZnS(1 0 0) substrate are studied in situ and with high lateral resolution using low energy electron microscopy (LEEM), micro low energy electron diffraction ( μLEED), x-ray photoemission electron microscopy (XPEEM), microprobe x-ray photoelectron spectroscopy ( μXPS) and x-ray magnetic circular dichroism PEEM (XMCDPEEM) for complementary structural, chemical, and magnetic characterization. Initially, a two-dimensional (Fe, Zn)S reaction layer forms with thickness that depends on growth temperature. Further growth results in the formation of a variety of three-dimensional crystals, most of them strongly elongated in the form of ‘nanowires’ of two distinct types, labeled as A and B. Type A nanowires are oriented near the ZnS[1 1 0] direction and are composed of Fe. Type B nanowires are oriented predominantly along directions a few degrees off the ZnS[0 0 1] direction and are identified as Greigite (Fe3S4). Both types of nanowires are magnetic with Curie temperatures above 450 °C. The understanding of the reactive growth mechanism in this system that is provided by these investigations may help to develop growth methods for other elemental and transition metal chalcogenide nanostructures on ZnS and possibly on other II-VI semiconductor surfaces.

  14. The chemical mechanism of the limonene ozonolysis reaction in the SOA formation: A quantum chemistry and direct dynamic study

    NASA Astrophysics Data System (ADS)

    Sun, Tingli; Wang, Yudong; Zhang, Chenxi; Sun, Xiaomin; Wang, Wenxing

    2011-03-01

    The ozonolysis of limonene is one of the most important processes for secondary organic aerosol formation and a detailed understanding of the atmospheric chemistry of d-limonene is highly urgent. In this paper, the reaction of d-limonene with O 3 has been studied using high level molecular orbital theory. A detailed description of the possible ozonolysis mechanism in the presence of H 2O or NO is provided. The main products obtained are keto-limonene, limononic acid and 7OH-lim, which are low vapor pressure compounds. On the basis of the quantum chemical information, the direct dynamic calculation is performed and the rate constants are calculated over a temperature range of 200˜800 K using the transition state theory and canonical varitional transition state theory with small-curvature tunneling effect. The four-parameter formula of rate constants with the temperature is fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information to the model simulation study.

  15. Formation of submicron magnesite during reaction of natural forsterite in H2O-saturated supercritical CO2

    NASA Astrophysics Data System (ADS)

    Qafoku, Odeta; Hu, Jianzhi; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in bulk liquid water saturated with supercritical CO2 (scCO2) and scCO2 saturated with water at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3·3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In liquid water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in scCO2 saturated with H2O magnesite formation was identified at all three temperatures: 35, 50, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 and 80 °C, but nesquehonite was dominant at 35 °C. The magnesite particles formed under scCO2 saturated with H2O conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with nucleation and growth on the forsterite surface.

  16. Enhanced reactivity of hydroxylated polycyclic aromatic hydrocarbons to birnessite in soil: reaction kinetics and nonextractable residue formation.

    PubMed

    Jung, Jae-Woong; Lee, Seunghwan; Ryu, Hyerim; Nam, Kyoungphile; Kang, Ki-Hoon

    2008-05-01

    Phenanthrene and pyrene were not transformed by birnessite (delta-MnO2) in the presence of phenol. The phenoxy radicals generated from phenol by birnessite did not act as a mediator for polycyclic aromatic hydrocarbon radical reaction under the studied conditions. In contrast, 9-hydroxyphenanthrene and 1-hydroxypyrene were remarkably sensitive to birnessite. The disappearance patterns of the test compounds both in the aqueous phase and soil followed first-order kinetics, with a linear relationship found between the rate constants and the surface area of birnessite. Moreover, the data indicated that the reaction was faster in the presence of soil than in the aqueous phase probably because of the presence of hydroxyl groups in soil organic matter. Sequential solvent extraction was not successful in the recovery of 9-hydroxyphenanthrene from the birnessite-treated soil samples, and capillary electrophoresis data suggest the formation of nonextractable residues of the compound in soil. In addition, the acute toxicity determined by Microtox declined approximately 8.3 times in the soil samples treated with birnessite compared to untreated samples, demonstrating that the toxic compound was no longer present as its parent form. PMID:18419188

  17. Formation of Submicron Magnesite during Reaction of Natural Forsterite in H2O-Saturated Supercritical CO2

    SciTech Connect

    Qafoku, Odeta; Hu, Jian Z.; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in a) liquid water saturated with supercritical CO2 (scCO2) and in b) H2O-saturated scCO2 at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3.3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in H2O-saturated scCO2 magnesite formation was identified at all three temperatures: 35 °, 50 °, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 ° and 80 °C; but nesquehonite was dominant at 35 °C. The magnesite particles formed under H2O-saturated scCO2 conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with epitaxial nucleation and growth on the forsterite surface.

  18. Formation of radical-anions and radicals in the reaction of sodium sulfide with aromatic halogen compounds

    SciTech Connect

    Annenkova, V.Z.; Antonik, L.M.; Vakul'skaya, T.I.; Voronkov, M.G.

    1986-03-20

    The ESR and UV spectroscopic methods were used to establish the mechanism of the substitution of a chlorine atom by sulfide sulfur in the reactions of 2,5-dichloro-nitrobenzene (i) and p-dichlorobenzene (II) with sodium sulfide in N-methyl-2-pyrrolidone. The S/sub 2//sup -./ and S/sub 3//sup -./ radical-anions were detected and identified. The former corresponds to a narrow singlet with a g factor of 2.005 (lambdamax 440 nm), while the latter corresponds to a broad ESR signal with a g value of 2.028 (lambdamax 618 nm) (1-3). The formation of the radical-anion of the reagent gave grounds for supposing that the reaction of (I) and (II) with sodium sulfide takes place through a one-electron transfer stage. Thus, a stable radical-anion characterized by hyperfine structure (hfs) (3/sub N/ x 2/sub H/ x 3/sub H/ x 3/sub H/ with constants of 11.6, 3.7, 3.5, and 0.7 Oe respectively) is formed in the nitrobenzene-sodium sulfide system.

  19. Facile Formation of a DNA Adduct of Semicarbazide on Reaction with Apurinic/Apyrimidinic Sites in DNA.

    PubMed

    Wang, Yinan; Chan, Ho Wai; Chan, Wan

    2016-05-16

    Mutagenic semicarbazide (SEM) is a hydrazine-containing food contaminant found in a wide variety of foods. Despite decades of research, the toxicity of SEM remains incompletely understood. In this study, we demonstrate for the first time that SEM reacts rapidly with apurinic/apyrimidinic sites in an endogenous DNA lesion to form covalently bonded DNA adducts in vitro and in bacteria. Specifically, we performed high-performance liquid chromatography with high accuracy and tandem mass spectrometry to characterize the DNA adduct formed by reacting SEM with 2'-deoxyribose and single- and double-stranded oligonucleotides containing abasic sites under physiologically relevant conditions. By analyzing the reaction mixture at different time points, the reaction kinetics of SEM with DNA was also elucidated. Moreover, by using a highly sensitive and selective liquid chromatography-tandem mass spectrometry method, we show that SEM induces the dose-dependent formation of DNA adducts in Escherichia coli. The results from our studies provide the first direct evidence suggesting that SEM may exert genotoxicity by forming covalently bonded DNA adducts. PMID:27058397

  20. Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution.

    PubMed

    Pereira, José Clayston Melo; Iretskii, Alexei V; Han, Rui-Min; Ford, Peter C

    2015-01-14

    Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 × 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(•) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes. PMID:25479566

  1. Study of the Reaction Cl + Ethyl Formate at 700-950 Torr and 297 to 435 K: Product Distribution and the Kinetics of the Reaction C2H5OC(═O) → CO2 + C2H5.

    PubMed

    Kaiser, E W

    2016-05-26

    The kinetics and mechanism of the reaction of atomic chlorine with ethyl formate [Cl + CH3CH2O(C═O)H, reaction 1] have been examined. These experiments were performed at pressures of 760-950 Torr and temperatures from 297 to 435 K. Reactants and products were quantified by gas chromatography-flame ionization detector (GC/FID) analysis. The initial mixture contained ethyl formate, Cl2, and N2. Cl atoms were generated by UV photolysis of this initial mixture at 360 nm, which dissociates Cl2. The rate constant of reaction 1 was measured at 297 K relative to that of the reaction Cl + C2H5Cl (reaction 2), yielding the rate constant ratio k1/k2 = 1.09 ± 0.05. The final products formed from reaction 1 are ethyl chloroformate, 1-chloroethyl formate, and 2-chloroethyl formate. These products result from the reactions with Cl2 of the three free radicals formed by H atom abstraction from ethylformate in reaction 1. Based on the molar yields of these three chlorinated products, the yields of the three radicals formed from reaction 1 at 297 K are (25 ± 3) mole percent of CH3CH2O(C═O); (67 ± 5) mole percent of CH3CHO(C═O)H; and (8 ± 2) mole percent of CH2CH2O(C═O)H. A second phase of this experiment measured the rate constant of the decarboxylation of the ethoxy carbonyl radical [CH3CH2O(C═O) → CO2 + C2H5, reaction 4] relative to the rate constant of its reaction with Cl2 [CH3CH2O(C═O) + Cl2 → CH3CH2O(C═O)Cl + Cl, reaction 3a]. Over the temperature range 297 to 404 K at 1 atm total pressure, this ratio can be expressed by k4/k3a = 10(23.56±0.22) e(-(12700±375)/RT) molecules cm(-3). Estimating the value of k3a (which has not been measured) based on similar reactions, the expression k4 = 5.8 × 10(12) e(-(12700)/RT) s(-1) is obtained. The estimated error of this rate constant is ± a factor of 2 over the experimental temperature range. This rate expression is compared with recent ab initio calculations of the decarboxylation of the analogous methoxy

  2. Switch and template pattern formation in a discrete reaction-diffusion system inspired by the Drosophila eye

    PubMed Central

    Pennington, Matthew W.; Lubensky, David K.

    2011-01-01

    We examine a spatially discrete reaction diffusion model based on the interactions that create a periodic pattern in the Drosophila eye imaginal disc. This model is known to be capable of generating a regular hexagonal pattern of gene expression behind a moving front, as observed in the fly system. In order to better understand the novel “switch and template” mechanism behind this pattern formation, we present here a detailed study of the model's behavior in one dimension, using a combination of analytic methods and numerical searches of parameter space. We find that patterns are created robustly provided that there is an appropriate separation of timescales and that self-activation is sufficiently strong, and we derive expressions in this limit for the front speed and the pattern wavelength. Moving fronts in pattern-forming systems near an initial linear instability generically select a unique pattern, but our model operates in a strongly nonlinear regime where the final pattern depends on the initial conditions as well as on parameter values. Our work highlights the important role that cellularization and cell-autonomous feedback can play in biological pattern formation. PMID:20862598

  3. Formation and Self-assembly of Gold Nanoplates through an Interfacial Reaction for Surface-Enhanced Raman Scattering.

    PubMed

    Ma, Ying; Yung, Lin-Yue Lanry

    2016-06-22

    3D hierarchical architectures assembled from individual particles have attracted great interest because they displayed novel properties from the individual building blocks as well as their complex structures. Here we present a new strategy to form 3D hierarchical gold (Au) nanostructures via an interfacial reduction reaction. An aniline (ANI) derivative, N-(3-amidino)-aniline (NAAN), and HAuCl4 were separately dissolved in toluene and water to form an organic/water interface. Au nanoplates formed at the interface and subsequently moved to the aqueous phase. As a capping agent for the nanoplate formation, the oxidized NAAN, i.e., poly(N-(3-amidino)-aniline) (PNAAN), also facilitated the self-assembly of Au nanoplates into 3D hierarchical Au nanoflowers (AuNFs) through π-π stacking. The individual AuNF exhibited good surface-enhanced Raman scattering (SERS) response both in enhancement factor and reproducibility because it integrates the SERS enhancement effects of individual Au nanoplates and their hierarchical structures. This is the first report depicting the one-pot formation and self-assembly of Au nanoplates into 3D organized hierarchical nanostructures through the molecular interaction of conducting polymer. PMID:27276116

  4. Entrance-channel mass-asymmetry dependence of compound nucleus formation time in light heavy-ion reactions

    SciTech Connect

    Szanto de Toledo, A.; Carlson, B.V.; Beck, C.

    1996-12-01

    The entrance-channel mass-asymmetry dependence of the compound nucleus formation time in light heavy-ion reactions has been investigated within the framework of semiclassical dissipative collision models. The model calculations have been applied successfully to the formation of the {sup 38}Ar compound nucleus as populated via the {sup 9}Be+{sup 29}Si, {sup 11}B+{sup 27}Al, {sup 12}C+{sup 26}Mg, and {sup 19}F+{sup 19}F entrance channels. The shape evolution of several other light composite systems appears to be consistent with the so-called {open_quote}{open_quote}Fusion Inhibition Factor{close_quote}{close_quote} which has been observed experimentally. As found previously in more massive systems for the fusion-evaporation process, the entrance-channel mass-asymmetry degree of freedom appears to determine the competition between the different mechanisms as well as the time scales involved. {copyright} {ital 1996 The American Physical Society.}

  5. Reactive geothermal transport simulation to study the formation mechanism of impermeable barrier between acidic and neutral fluid zones in the Onikobe geothermal field, Japan

    SciTech Connect

    Todaka, Noritumi; Akasaka, Chitosi; Xu, Tianfu; Pruess, Karsten

    2003-03-06

    Two types of fluids are encountered in the Onikobe geothermal reservoir (Japan): One is neutral and the other is acidic. It is hypothesized that acidic fluid might be upwelling along a fault zone from magma and that an impermeable barrier might be present between the acidic and neutral fluid zones. To test such a conceptual model and to study the geochemical behavior due to mixing of the two fluids, reactive geothermal transport simulations under both natural and production conditions were carried out using the code TOUGHREACT. Results indicate Mn-rich smectite precipitates near the mixing front. Precipitation of sphalerite and galena occurs in a similar region as the Mn-rich smectite. Precipitation of these minerals depends on pH and temperature. In addition, quartz, pyrite, and calcite precipitate in the shallow zone resulting in further development of caprock. The changes in porosity and permeability due to precipitation of Mn-rich smectite are small compared with that of quartz, calcite, and pyrite. However, the smectite precipitation is likely to fill open fractures and to form an impermeable barrier between acidic and neutral fluid regions. The simulated mineral assemblage is generally consistent with observations in the Onikobe field. The numerical simulations described here provide useful insight into geochemical behavior and formation of impermeable barriers from fluid mixing. The method presented in this paper may be useful in fundamental analysis of hydrothermal systems and in the exploration of geothermal reservoirs, including chemical evolution, mineral alteration, mineral scaling, and changes in porosity and permeability.

  6. Reactive geothermal transport simulations to study the formation mechanism of an impermeable barrier between acidic and neutral fluid zones in the Onikobe Geothermal Field, Japan

    NASA Astrophysics Data System (ADS)

    Todaka, Norifumi; Akasaka, Chitoshi; Xu, Tianfu; Pruess, Karsten

    2004-05-01

    Two types of fluids are encountered in the Onikobe geothermal reservoir (Japan): one is neutral and the other is acidic. It is hypothesized that acidic fluid might be upwelling along a fault zone from magma and that an impermeable barrier might be present between the acidic and neutral fluid zones. To test such a conceptual model and to study the geochemical behavior due to mixing of the two fluids, reactive geothermal transport simulations under both natural and production conditions were carried out using the code TOUGHREACT. Results indicate Mn-rich smectite precipitates near the mixing front. Precipitation of sphalerite and galena occurs in a similar region as the Mn-rich smectite. Precipitation of these minerals depends on pH and temperature. In addition, quartz, pyrite, and calcite precipitate in the shallow zone resulting in further development of caprock. The changes in porosity and permeability due to precipitation of Mn-rich smectite are small compared with that of quartz, calcite, and pyrite. However, the smectite precipitation is likely to fill open fractures and to form an impermeable barrier between acidic and neutral fluid regions. The simulated mineral assemblage is generally consistent with observations in the Onikobe field. The numerical simulations described here provide useful insight into geochemical behavior and formation of impermeable barriers from fluid mixing. The method presented in this paper may be useful in fundamental analysis of hydrothermal systems and in the exploration of geothermal reservoirs, including chemical evolution, mineral alteration, mineral scaling, and changes in porosity and permeability.

  7. Description of fusion and evaporation residue formation cross sections in reactions leading to the formation of element Z =122 within the Langevin approach

    NASA Astrophysics Data System (ADS)

    Litnevsky, V. L.; Kosenko, G. I.; Ivanyuk, F. A.

    2016-06-01

    We describe the evolution of the compact system formed by the touching of two colliding ions in reactions 58Fe+248Cm → 306-x122 + xn, 64Ni+244Pu → 308-x122 + xn, and 90Zr+208Pb → 298-x122 + xn. The description is carried out within the dynamical multidimensional stochastic approach, based on Langevin equations for the shape degrees of freedom of colliding ions and the compact system. For the approach stage we take into account the shell structure of colliding ions, their orientation in the space, and the effect of tunneling of ions through the Coulomb barrier. By describing the evolution of the compact system formed after the touching of incident ions, the shell structure of the compact system is also taken into account. Within this approach we have calculated the compound nucleus and evaporation residue formation cross sections. These can be compared with the experimental data. We have also clarified the impact of the tunneling effect in the entrance channel on the fusion and evaporation residue cross sections.

  8. The secondary formation of inorganic aerosols in the droplet mode through heterogeneous aqueous reactions under haze conditions

    NASA Astrophysics Data System (ADS)

    Wang, Xinfeng; Wang, Wenxing; Yang, Lingxiao; Gao, Xiaomei; Nie, Wei; Yu, Yangchun; Xu, Pengju; Zhou, Yang; Wang, Zhe

    2012-12-01

    Secondary inorganic aerosols play important roles in visibility reduction and in regional haze pollution. To investigate the characteristics of size distributions of secondary sulfates and nitrates as well as their formation mechanisms under hazes, size-resolved aerosols were collected using a Micro-Orifice Uniform Deposit Impactor (MOUDI) at an urban site in Jinan, China, in all four seasons (December 2007-October 2008). In haze episodes, the secondary sulfates and nitrates primarily formed in fine particles, with elevated concentration peaks in the droplet mode (0.56-1.8 μm). The fine sulfates and nitrates were completely neutralized by ammonia and existed in the forms of (NH4)2SO4 and NH4NO3, respectively. The secondary formation of sulfates, nitrates and ammonium (SNA) was found to be related to heterogeneous aqueous reactions and was largely dependent on the ambient humidity. With rising relative humidity, the droplet-mode SNA concentration, the ratio of droplet-mode SNA to the total SNA, the fraction of SNA in droplet-mode particles and the mass median aerodynamic diameter of SNA presented an exponential, logarithmic or linear increase. Two heavily polluted multi-day haze episodes in winter and summer were analyzed in detail. The secondary sulfates were linked to heterogeneous uptake of SO2 followed by the subsequent catalytic oxidation by oxygen together with iron and manganese in winter. The fine nitrate formation was strongly associated with the thermodynamic equilibrium among NH4NO3, gaseous HNO3 and NH3, and showed different temperature-dependences in winter and summer.

  9. Model of unidirectional block formation leading to reentrant ventricular tachycardia in the infarct border zone of postinfarction canine hearts

    PubMed Central

    Ciaccio, Edward J.; Coromilas, James; Ashikaga, Hiroshi; Cervantes, Daniel O.; Wit, Andrew L.; Peters, Nicholas S.; McVeigh, Elliot R.; Garan, Hasan

    2015-01-01

    Background When the infarct border zone is stimulated prematurely, a unidirectional block line (UBL) can form and lead to double-loop (figure-of-eight) reentrant ventricular tachycardia (VT) with a central isthmus. The isthmus is composed of an entrance, center, and exit. It was hypothesized that for certain stimulus site locations and coupling intervals, the UBL would coincide with the isthmus entrance boundary, where infarct border zone thickness changes from thin-to-thick in the travel direction of the premature stimulus wavefront. Method A quantitative model was developed to describe how thin-to-thick changes in the border zone result in critically convex wavefront curvature leading to conduction block, which is dependent upon coupling interval. The model was tested in 12 retrospectively analyzed postinfarction canine experiments. Electrical activation was mapped for premature stimulation and for the first reentrant VT cycle. The relationship of functional conduction block forming during premature stimulation to functional block during reentrant VT was quantified. Results For an appropriately placed stimulus, in accord with model predictions: (1) The UBL and reentrant VT isthmus lateral boundaries overlapped (error: 4.8±5.7 mm). (2) The UBL leading edge coincided with the distal isthmus where the center-entrance boundary would be expected to occur. (3) The mean coupling interval was 164.6±11.0 ms during premature stimulation and 190.7±20.4 ms during the first reentrant VT cycle, in accord with model calculations, which resulted in critically convex wavefront curvature with functional conduction block, respectively, at the location of the isthmus entrance boundary and at the lateral isthmus edges. Discussion Reentrant VT onset following premature stimulation can be explained by the presence of critically convex wavefront curvature and unidirectional block at the isthmus entrance boundary when the premature stimulation interval is sufficiently short. The

  10. Global hydromagnetic simulations of a planet embedded in a dead zone: Gap opening, gas accretion, and formation of a protoplanetary jet

    SciTech Connect

    Gressel, O.; Nelson, R. P.; Turner, N. J.; Ziegler, U. E-mail: r.p.nelson@qmul.ac.uk E-mail: uziegler@aip.de

    2013-12-10

    We present global hydrodynamic (HD) and magnetohydrodynamic (MHD) simulations with mesh refinement of accreting planets embedded in protoplanetary disks (PPDs). The magnetized disk includes Ohmic resistivity that depends on the overlying mass column, leading to turbulent surface layers and a dead zone near the midplane. The main results are: (1) the accretion flow in the Hill sphere is intrinsically three-dimensional for HD and MHD models. Net inflow toward the planet is dominated by high-latitude flows. A circumplanetary disk (CPD) forms. Its midplane flows outward in a pattern whose details differ between models. (2) The opening of a gap magnetically couples and ignites the dead zone near the planet, leading to stochastic accretion, a quasi-turbulent flow in the Hill sphere, and a CPD whose structure displays high levels of variability. (3) Advection of magnetized gas onto the rotating CPD generates helical fields that launch magnetocentrifugally driven outflows. During one specific epoch, a highly collimated, one-sided jet is observed. (4) The CPD's surface density is ∼30 g cm{sup −2}, small enough for significant ionization and turbulence to develop. (5) The accretion rate onto the planet in the MHD simulation reaches a steady value 8 × 10{sup –3} M {sub ⊕} yr{sup –1} and is similar in the viscous HD runs. Our results suggest that gas accretion onto a forming giant planet within a magnetized PPD with a dead zone allows rapid growth from Saturnian to Jovian masses. As well as being relevant for giant planet formation, these results have important implications for the formation of regular satellites around gas giant planets.

  11. Towards quantifying the reaction network around the sulfate–methane-transition-zone in the Ulleung Basin, East Sea, with a kinetic modeling approach

    SciTech Connect

    Hong, Wei-Li; Torres, Marta E.; Kim, Ji-Hoon; Choi, Jiyoung; Bahk, Jang-Jun

    2014-09-01

    We present a kinetic model based upon pore water data collected from eight sites drilled during the second Ulleung Basin gas hydrate drilling expedition (UBGH2) in 2010. Three sites were drilled at locations where acoustic chimneys were identified in seismic data, and the rest were drilled on non-chimney (i.e. background) environments. Our model, coupled a comprehensive compositional and isotopic data set, is used to illustrate the different biogeochemical processes at play in those two environments, in terms of reactions around the sulfate-methane-transition-zone (SMTZ). Organic matter decomposition is an important process for production of methane, dissolved inorganic carbon (DIC) and consumption of sulfate in the non-chimney sites, whereas anaerobic oxidation of methane (AOM) dominates both carbon and sulfur cycles in the chimney environment. Different sources of methane mediate AOM in the two settings. Internally produced methane through CO₂ reduction (CR) and methanogenesis fuels AOM in the non-chimney sites, whereas AOM is sustained by methane from external sources in the chimney sites. We also simulate the system evolution from non-chimney to chimney conditions by increasing the bottom methane supply to a non-chimney setting. We show that the higher CH₄ flux leads to a higher microbial activity of AOM, and more organic matter decomposition through methanogenesis. A higher methanogenesis rate and a smaller CR contribution relative to AOM in the chimney sites is responsible for the isotopically light DIC and heavy methane in this environment, relative to the non-chimney sites.

  12. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    NASA Astrophysics Data System (ADS)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  13. Kinetics and mechanism of formation of chlorate ion from the hypochlorous acid/chlorite ion reaction at pH 6-10

    SciTech Connect

    Gordon, G.; Tachiyashiki, Satoshi )

    1991-03-01

    The reaction between free chlorine (HOCl/OCl{sup {minus}}) and chlorite ion (ClO{sub 2}{sup {minus}}) has been studied in the pH 6.4-10.0 region. The reaction proceeds through the Cl{sub 2}O{sub 2} intermediate followed by a direct reaction of the intermediate with hypochlorous acid to form chlorate ion. Time-concentration profiles were measured for each chlorine species, resulting in both total chlorine and redox balance. Negligibly small amounts of chlorine dioxide are formed above pH 7. Indirect evidence suggests that, in this pH region, the formation of any chlorine dioxide is primarily due to the presence of concentration gradients or because of the adventitious presence of catalytic metal ion impurities. Details of the overall reaction mechanism for the formation of chlorate ion are presented.

  14. 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. PMID:27307079

  15. Formative Processes of a Sliding Zone in Pelitic Schist - Implications of Microscopic Analyses on High-quality Drilled Cores

    NASA Astrophysics Data System (ADS)

    Yamasaki, S.; Chigira, M.

    2009-04-01

    Pelitic schist has been known to be easily deformed by gravitational force to form characteristic topographic and geologic features, but little is known about how they develop. This is mainly due to the fact that deformed politic schist is so fragile that it could not be obtained from subsurface without disturbance. We analyzed high-quality undisturbed cores obtained by using a sophisticated drilling technique from two typical pelitic schist landslide sites in Japan. We made analyses on physical, chemical, mineralogical properties and observations from mesoscopic to microscopic rock textures of these cores and found that a special layering of rock-forming minerals determines the locations of shearing by gravity and that there is specific water-rock interaction processes in pelitic schist. Pelitic schist consists of thinly alternating beds of black layers and quartz-rich layers, and a black layer has numerous microscopic layers containing abundant pyrite and graphite grains (pyrite-graphite layers). Many of the black layers were observed to have microfractures connected to open cracks, suggesting that relatively thick, continuous black layers are easily sheared to form an incipient sliding layer. Thus unevenly distributed pyrite-graphite layers likely to determine the potential location of microscopic slip in a rock mass. Shear displacement along black layers occurs unevenly, depending upon the microscopic heterogeneity in mineral composition as well as undulating shape of the layers. Open micro-cracks nearly perpendicular to the schistosity were commonly observed in quartz-rich layers in contact with black layers, suggesting that the shearing occurred with heterogeneous displacements along the black layer and that it occurred under the low confining pressure. This is in the incipient stage of a fracture zone. When shearing occurs along two thick neighboring black layers, the rock in between would be fractured, rotated and pulverized. In some cases, quartz

  16. Reaction of ClO with NO[sub 3]: OClO formation and night-time O[sub 3] loss

    SciTech Connect

    Toumi, R. )

    1994-06-22

    The author presents the results of a model study of the atmospheric chemistry of ClO with NO[sub 3]. No effort is made to consider heterogeneous reactions on polar stratospheric cloud nuclei for example. There seem to be two major product channels. One results in the formation of Cl and NO[sub 2], and is able to contribute to catalytic ozone destruction of ozone in the lower stratosphere at night. The other process results in OClO formation at night, and is a major source of this molecule in the upper stratosphere. For the arctic this reaction does not make a significant contribution in the lower stratosphere.

  17. A restricted period for formation of outer subventricular zone defined by Cdh1 and Trnp1 levels

    PubMed Central

    Martínez-Martínez, Maria Ángeles; De Juan Romero, Camino; Fernández, Virginia; Cárdenas, Adrián; Götz, Magdalena; Borrell, Víctor

    2016-01-01

    The outer subventricular zone (OSVZ) is a germinal layer playing key roles in the development of the neocortex, with particular relevance in gyrencephalic species such as human and ferret, where it contains abundant basal radial glia cells (bRGCs) that promote cortical expansion. Here we identify a brief period in ferret embryonic development when apical RGCs generate a burst of bRGCs that become founders of the OSVZ. After this period, bRGCs in the OSVZ proliferate and self-renew exclusively locally, thereby forming a self-sustained lineage independent from the other germinal layers. The time window for the brief period of OSVZ bRGC production is delineated by the coincident downregulation of Cdh1 and Trnp1, and their upregulation reduces bRGC production and prevents OSVZ seeding. This mechanism in cortical development may have key relevance in brain evolution and disease. PMID:27264089

  18. A restricted period for formation of outer subventricular zone defined by Cdh1 and Trnp1 levels.

    PubMed

    Martínez-Martínez, Maria Ángeles; De Juan Romero, Camino; Fernández, Virginia; Cárdenas, Adrián; Götz, Magdalena; Borrell, Víctor

    2016-01-01

    The outer subventricular zone (OSVZ) is a germinal layer playing key roles in the development of the neocortex, with particular relevance in gyrencephalic species such as human and ferret, where it contains abundant basal radial glia cells (bRGCs) that promote cortical expansion. Here we identify a brief period in ferret embryonic development when apical RGCs generate a burst of bRGCs that become founders of the OSVZ. After this period, bRGCs in the OSVZ proliferate and self-renew exclusively locally, thereby forming a self-sustained lineage independent from the other germinal layers. The time window for the brief period of OSVZ bRGC production is delineated by the coincident downregulation of Cdh1 and Trnp1, and their upregulation reduces bRGC production and prevents OSVZ seeding. This mechanism in cortical development may have key relevance in brain evolution and disease. PMID:27264089

  19. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

    ERIC Educational Resources Information Center

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  20. Influence of mineral dust mixing-state and reaction probabilities on size-resolved sulfate formation in Northeast Asia

    NASA Astrophysics Data System (ADS)

    Song, C. H.; Nam, J. E.; Han, K. M.; Lee, M. K.; Woo, J. H.; Han, J. S.

    2012-10-01

    Significant differences were found between two particulate sulfate size-distributions measured using a MOUDI impactor at Gosan, Jeju Island, Korea, and simulated via the Lagrangian photochemical model under a condition of aerosol internal mixing between mineral dust and urban pollution particles. It was suspected that these differences might have resulted from: (1) the assumption of aerosol internal mixing and (2) the uses of identical reaction probabilities (γ) of the gaseous sulfate precursors (SO2 and H2SO4) onto both urban pollution particles and mineral dust in the Lagrangian photochemical model simulations. In this study; therefore, some cases of aerosol external mixing between urban-derived pollution aerosols and mineral dust were investigated, with different magnitudes of γ for the gas-phase sulfate precursors onto the two different condensing media. The model simulations under the external mixing condition, with different magnitudes of the reaction probabilities (γi,urban and γi,dust) onto urban pollution particles and mineral dust, successfully reproduced the size-dependent particulate sulfate formation measured at the Gosan station. Further attempts were made to approximate the magnitudes of γSO2,urban and γH2SO4,dust under external mixing state conditions with the fixed γSO2,dust and γH2SO2,urban values of 10-4 and 1.0. The best-estimates of γSO2,urban and γH2SO4,dust found in this study were in the orders of 10-4-10-5 and 10-2-10-3, respectively.

  1. Experimental study on the effect of SO2 on PCDD/F emissions: determination of the importance of gas-phase versus solid-phase reactions in PCDD/F formation.

    PubMed

    Ryan, Shawn P; Li, Xiao-Dong; Gullett, Brian K; Lee, C W; Clayton, Matt; Touati, Abderrahmane

    2006-11-15

    Cofiring coal in municipal solid waste incinerators (MSWls) has previously been reported to reduce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) emissions due to increasing the flue gas SO2 concentration. The present study was focused on understanding the primary mechanism responsible for the suppressant effect of SO2 on total PCDD/F formation and toxic equivalent (TEQ) emissions. The addition of SO2, simulating the effect of coal addition on the flue gas composition, resulted in significant reductions in the TEQ emissions due to reactions involving SO2 in the postcombustion zone. However, emissions of total PCDDs/Fs, unlike the TEQ value, were dependent upon the Cl2 and SO2 injection temperatures due to increases in non-TEQ correlated isomers. The conversion of metal chlorides in the fly ash to sulfates, thus reducing the sites responsible for chlorination/oxidation reactions, was concluded to be the main suppressant mechanism; proposed reactions for copper and iron are presented. This mechanism was found to be independent of combustion conditions and could have prolonged effects on PCDD/F emissions from deposits formed with high flue gas S/Cl ratios. PMID:17154014

  2. Water-Organic-Rock Reactions Recorded in Pores in Shales from the Marcellus and Rose Hill Formations (Invited)

    NASA Astrophysics Data System (ADS)

    Brantley, S. L.; Jin, L.; Rother, G.; Cole, D. R.; gu, X.; Balashov, V. N.

    2013-12-01

    The porosity of shales varies depending upon such attributes as the mineralogy, grain size, organic content, depth and duration of burial, and extent of water-rock reaction. Today, shales are being exploited when they contain significant natural gas, and the connectivity of pores are important toward controlling both recovery of gas after hydrofracking. In fact, the fine-scale nature of the pores controls aspects of release of natural gas and brines during hydrofracturing and gas exploitation. Despite the importance of shale as a source rock for natural gas and petroleum, it remains difficult to quantify and image porosity in shales because of their fine-scale nature. We are using neutron scattering, FIB SEM, CT microtomography, and other techniques to understand pores in a black (Marcellus) and a grey shale (Rose Hill formation) sampled in Pennsylvania. Samples were recovered both from outcrop and from depth in wellbores. We also report a new approach for investigating pores in shales by using neutron scattering before and after removal of organic matter. Pores in the two shales are observed to be isotropic (i.e. in the plane of bedding) or anisotropic (i.e. perpendicular to bedding), as expected for sediments that have been compacted after burial. Some nanometer-sized pores are observed in the organic matter of the Marcellus to be spherical; other pores are observed to be present in pyrite framboids and among silicate grains in that rock. We have no evidence that significant porosity is present in the organic matter in the Rose Hill formation, a relatively organic-poor shale, but pores are observed between and in clay particles. We also investigate how progressive water-rock reaction changes the primary porosity in the shales by investigating weathering samples. FIB SEM images document that organic matter is oxidized and removed significantly from the weathering Marcellus before the rock turns to soil, leaving behind porosity. Pyrite oxidation and dissolution

  3. Atomistically determined phase-field modeling of dislocation dissociation, stacking fault formation, dislocation slip, and reactions in fcc systems

    NASA Astrophysics Data System (ADS)

    Rezaei Mianroodi, Jaber; Svendsen, Bob

    2015-04-01

    The purpose of the current work is the development of a phase field model for dislocation dissociation, slip and stacking fault formation in single crystals amenable to determination via atomistic or ab initio methods in the spirit of computational material design. The current approach is based in particular on periodic microelasticity (Wang and Jin, 2001; Bulatov and Cai, 2006; Wang and Li, 2010) to model the strongly non-local elastic interaction of dislocation lines via their (residual) strain fields. These strain fields depend in turn on phase fields which are used to parameterize the energy stored in dislocation lines and stacking faults. This energy storage is modeled here with the help of the "interface" energy concept and model of Cahn and Hilliard (1958) (see also Allen and Cahn, 1979; Wang and Li, 2010). In particular, the "homogeneous" part of this energy is related to the "rigid" (i.e., purely translational) part of the displacement of atoms across the slip plane, while the "gradient" part accounts for energy storage in those regions near the slip plane where atomic displacements deviate from being rigid, e.g., in the dislocation core. Via the attendant global energy scaling, the interface energy model facilitates an atomistic determination of the entire phase field energy as an optimal approximation of the (exact) atomistic energy; no adjustable parameters remain. For simplicity, an interatomic potential and molecular statics are employed for this purpose here; alternatively, ab initio (i.e., DFT-based) methods can be used. To illustrate the current approach, it is applied to determine the phase field free energy for fcc aluminum and copper. The identified models are then applied to modeling of dislocation dissociation, stacking fault formation, glide and dislocation reactions in these materials. As well, the tensile loading of a dislocation loop is considered. In the process, the current thermodynamic picture is compared with the classical mechanical

  4. Formation of silylgermane by a silylene insertion reaction in the infrared photochemistry of monosilane-monogermane mixtures

    SciTech Connect

    Zhu, P.; Piserchio, M.; Lampe, F.W.

    1985-12-05

    The infrared photodecomposition at 944.2 cm/sup -1/ of silane-germane mixtures has been studied over a pressure range of 24-46 torr and over a temperature range of 295-356 K. The products observed are hydrogen, disilane, silylgermane, trace amounts of trisilane, and solid polymeric material. Digermane formation was not observed. The primary photodecomposition of SiH/sub 4/ is to SiH/sub 2/ + H/sub 2/; this is followed by insertion of SiH/sub 2/ into an Si-H bond of SiH/sub 4/ or a Ge-H bond of GeH/sub 4/ to form Si/sub 2/H/sub 6/ or SiH/sub 3/GeH/sub 3/, respectively. On the basis of these studies, the competitive rates of SiH/sub 3/GeH/sub 3/ and Si/sub 2/H/sub 6/ formation as a function of temperature and those in the literature relative to the absolute rate of insertion of SiH/sub 2/ into SiH/sub 4/, the value k/sub 2/ = 10/sup 10.4+/-0.5/ exp(-10.7 +/- 5.3 x 10/sup 3/ J/RT) L mol/sup -1/ s/sup -1/ for the specific reaction rate of insertion of SiH/sub 2/ into a Ge-H bond of germane is derived. 30 references, 4 figures.

  5. Hurricane Mountain Formation melange: history of Cambro-Ordovician accretion of the Boundary Mountains terrane within the northern Appalachian orthotectonic zone

    SciTech Connect

    Boone, G.M.; Boudette, E.L.

    1985-01-01

    The Hurricane Mountain Formation (HMF) melange and associated ophiolitic and volcanogenic formations of Cambrian and lowermost Ordovician age bound the SE margin of the Precambrian Y (Helikian) Chain Lakes Massif in western Maine. HMF melange matrix, though weakly metamorphosed, contains a wide variety of exotic greenschist to amphibolite facies blocks as components of its polymictic assemblage, but blocks of high-grade cratonal rocks such as those of Chain Lakes or Grenville affinity are lacking. Formations of melange exposed in structural culminations of Cambrian and Ordovician rocks NE of the HMF in Maine and in the Fournier Group in New Brunswick are lithologically similar and probably tectonically correlative with the HMF; taken together, they may delineate a common pre-Middle Ordovician tectonic boundary. The authors infer that the Hurricane Mountain and St. Daniel melange belts define the SE and NW margins of the Boundary Mountains accreted terrane (BMT), which may consist of cratonal basement of Chain Lakes affinity extending from eastern Gaspe (deBroucker and St. Julien, 1985) to north-central New Hampshire. The Laurentian continental margin, underlain by Grenville basement, underplated the NW margin of this terrane, marked by the SDF suture zone, in late Cambrian to early Ordovician time, while terranes marked by Cambrian to Tremadocian (.) lithologies dissimilar to the Boundary Mountains terrane were accreted to its outboard margin penecontemporaneously. The docking of the Boundary Mountains terrane and the initiation of its peripheral melanges are equated to the Penobscottian disturbance.

  6. Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential thirdhand smoke hazards

    PubMed Central

    Sleiman, Mohamad; Gundel, Lara A.; Pankow, James F.; Jacob, Peyton; Singer, Brett C.; Destaillats, Hugo

    2010-01-01

    This study shows that residual nicotine from tobacco smoke sorbed to indoor surfaces reacts with ambient nitrous acid (HONO) to form carcinogenic tobacco-specific nitrosamines (TSNAs). Substantial levels of TSNAs were measured on surfaces inside a smoker’s vehicle. Laboratory experiments using cellulose as a model indoor material yielded a > 10-fold increase of surface-bound TSNAs when sorbed secondhand smoke was exposed to 60 ppbv HONO for 3 hours. In both cases we identified 1-(N-methyl-N-nitrosamino)-1-(3-pyridinyl)-4-butanal, a TSNA absent in freshly emitted tobacco smoke, as the major product. The potent carcinogens 4-(methylnitrosamino)-1-(3-pyridinyl)-1-butanone and N-nitroso nornicotine were also detected. Time-course measurements revealed fast TSNA formation, with up to 0.4% conversion of nicotine. Given the rapid sorption and persistence of high levels of nicotine on indoor surfaces—including clothing and human skin—this recently identified process represents an unappreciated health hazard through dermal exposure, dust inhalation, and ingestion. These findings raise concerns about exposures to the tobacco smoke residue that has been recently dubbed “thirdhand smoke.” Our work highlights the importance of reactions at indoor interfaces, particularly those involving amines and NOx/HONO cycling, with potential health impacts. PMID:20142504

  7. Anhydride formation is not a valid mechanism for peptide cleavage by carboxypeptidase-A: a semiempirical reaction pathway study

    NASA Astrophysics Data System (ADS)

    Vardi-Kilshtain, Alexandra; Shoham, Gil; Goldblum, Amiram

    The mechanism of action of zinc metalloproteinases has been studied by following the direct nucleophilic pathway, which has been frequently suggested but not yet examined by computational methods, and comparing it to other pathways. We computed the reaction enthalpies for the direct nucleophilic attack by Glu270 in the active site model of carboxypeptidase-A on a model substrate's peptide carbonyl and followed this pathway through mixed anhydride formation and subsequent anhydride cleavage by water. The starting molecular coordinates originate in our own high-resolution crystal structure and the computations have been conducted with the minimal neglect of differential overlap (MNDO) Hamiltonian, modified to include the d-orbitals of zinc and the effects of multiple hydrogen bonding, thus labelled MNDO/d/H. Compared to our recent results for two other candidate pathways for this mechanism, both of the General-Acid-General-Base type, we conclude that the direct nucleophilic or 'anhydride' pathway has a much higher energy barrier at the rate determining step, which is a proton transfer, than previously calculated paths. We argue that the 'anhydride' pathway is thus not a valid one for the cleavage of peptides by carboxypeptidase-A.

  8. Laser-filament-induced snow formation in a subsaturated zone in a cloud chamber: experimental and theoretical study.

    PubMed

    Ju, Jingjing; Sun, Haiyi; Sridharan, Aravindan; Wang, Tie-Jun; Wang, Cheng; Liu, Jiansheng; Li, Ruxin; Xu, Zhizhan; Chin, See Leang

    2013-12-01

    1 kHz, 2 mJ, 45 fs, 800 nm laser pulses were fired into a laboratory diffusion cloud chamber through a subsaturated zone (relative humidity ∼73%, T ∼ 4.3 °C). After 60 min of laser irradiation, an oval-shaped snow pile was observed right below the filament center and weighed ∼12.0 mg. The air current velocity at the edge of the vortices was estimated to be ∼16.5 cm/s. Scattering scenes recorded from the side show that filament-induced turbulence were formed inside the cloud chamber with two vortices below the filament. Two-dimensional simulations of the air flow motion in two cross sections of the cloud chamber confirm that the turbulent vortices exist below the filament. Based upon this simulation, we deduce that the vortices indeed have a three-dimensional elliptical shape. Hence, we propose that inside vortices where the humidity was supersaturated or saturated the condensation nuclei, namely, HNO(3), N(2)(+), O(2)(+) and other aerosols and impurities, were activated and grew in size. Large-sized particles would eventually be spun out along the fast moving direction towards the cold plate and formed an oval-shaped snow pile at the end. PMID:24483507

  9. Microstructure formation in partially melted zone during gas tungsten arc welding of AZ91 Mg cast alloy

    SciTech Connect

    Zhu Tianping Chen, Zhan W.; Gao Wei

    2008-11-15

    During gas tungsten arc (GTA) welding of AZ91 Mg cast alloy, constitutional liquid forms locally in the original interdendritic regions in the partially melted zone (PMZ). The PMZ re-solidification behaviour has not been well understood. In this study, the gradual change of the re-solidification microstructure within PMZ from base metal side to weld metal side was characterised. High cooling rate experiments using Gleeble thermal simulator were also conducted to understand the morphological change of the {alpha}-Mg/{beta}-Mg{sub 17}Al{sub 12} phase interface formed during re-solidification after partial melting. It was found that the original partially divorced eutectic structure has become a more regular eutectic phase in most of the PMZ, although close to the fusion boundary the re-solidified eutectic is again a divorced one. Proceeding the eutectic re-solidification, if the degree of partial melting is sufficiently high, {alpha}-Mg re-solidified with a cellular growth, resulting in a serrated interface between {alpha}-Mg and {alpha}-Mg/{beta}-Mg{sub 17}Al{sub 12} in the weld sample and between {alpha}-Mg and {beta}-Mg{sub 17}Al{sub 12} (fully divorced eutectic) in Gleeble samples. The morphological changes affected by the peak temperature and cooling rate are also explained.

  10. Towards quantifying the reaction network around the sulfate–methane-transition-zone in the Ulleung Basin, East Sea, with a kinetic modeling approach

    DOE PAGESBeta

    Hong, Wei-Li; Torres, Marta E.; Kim, Ji-Hoon; Choi, Jiyoung; Bahk, Jang-Jun

    2014-09-01

    We present a kinetic model based upon pore water data collected from eight sites drilled during the second Ulleung Basin gas hydrate drilling expedition (UBGH2) in 2010. Three sites were drilled at locations where acoustic chimneys were identified in seismic data, and the rest were drilled on non-chimney (i.e. background) environments. Our model, coupled a comprehensive compositional and isotopic data set, is used to illustrate the different biogeochemical processes at play in those two environments, in terms of reactions around the sulfate-methane-transition-zone (SMTZ). Organic matter decomposition is an important process for production of methane, dissolved inorganic carbon (DIC) and consumptionmore » of sulfate in the non-chimney sites, whereas anaerobic oxidation of methane (AOM) dominates both carbon and sulfur cycles in the chimney environment. Different sources of methane mediate AOM in the two settings. Internally produced methane through CO₂ reduction (CR) and methanogenesis fuels AOM in the non-chimney sites, whereas AOM is sustained by methane from external sources in the chimney sites. We also simulate the system evolution from non-chimney to chimney conditions by increasing the bottom methane supply to a non-chimney setting. We show that the higher CH₄ flux leads to a higher microbial activity of AOM, and more organic matter decomposition through methanogenesis. A higher methanogenesis rate and a smaller CR contribution relative to AOM in the chimney sites is responsible for the isotopically light DIC and heavy methane in this environment, relative to the non-chimney sites.« less

  11. Towards quantifying the reaction network around the sulfate-methane-transition-zone in the Ulleung Basin, East Sea, with a kinetic modeling approach

    NASA Astrophysics Data System (ADS)

    Hong, Wei-Li; Torres, Marta E.; Kim, Ji-Hoon; Choi, Jiyoung; Bahk, Jang-Jun

    2014-09-01

    We present a kinetic model based upon pore water data collected from eight sites drilled during the second Ulleung Basin gas hydrate drilling expedition (UBGH2) in 2010. Three sites were drilled at locations where acoustic chimneys were identified in seismic data, and the rest were drilled on non-chimney (i.e., background) environments. Our model, coupled a comprehensive compositional and isotopic data set, is used to illustrate the different biogeochemical processes at play in those two environments, in terms of reactions around the sulfate-methane-transition-zone (SMTZ). Organic matter decomposition is an important process for production of methane, dissolved inorganic carbon (DIC) and consumption of sulfate in the non-chimney sites, whereas anaerobic oxidation of methane (AOM) dominates both carbon and sulfur cycles in the chimney environment. Different sources of methane mediate AOM in the two settings. Internally produced methane through CO2 reduction (CR) and methanogenesis fuels AOM in the non-chimney sites, whereas AOM is sustained by methane from external sources in the chimney sites. We also simulate the system evolution from non-chimney to chimney conditions by increasing the bottom methane supply to a non-chimney setting. We show that the higher CH4 flux leads to a higher microbial activity of AOM, and more organic matter decomposition through methanogenesis. A higher methanogenesis rate and a smaller CR contribution relative to AOM in the chimney sites is responsible for the isotopically light DIC and heavy methane in this environment, relative to the non-chimney sites.

  12. Laser powder-bed fusion additive manufacturing: Physics of complex melt flow and formation mechanisms of pores, spatter, and denudation zones

    DOE PAGESBeta

    Khairallah, Saad A.; Anderson, Andrew T.; Rubenchik, Alexander; King, Wayne E.

    2016-02-23

    Our study demonstrates the significant effect of the recoil pressure and Marangoni convection in laser powder bed fusion (L-PBF) of 316L stainless steel. A three-dimensional high fidelity powder-scale model reveals how the strong dynamical melt flow generates pore defects, material spattering (sparking), and denudation zones. The melt track is divided into three sections: a topological depression, a transition and a tail region, each being the location of specific physical effects. The inclusion of laser ray-tracing energy deposition in the powder-scale model improves over traditional volumetric energy deposition. It enables partial particle melting, which impacts pore defects in the denudation zone.more » Different pore formation mechanisms are observed at the edge of a scan track, at the melt pool bottom (during collapse of the pool depression), and at the end of the melt track (during laser power ramp down). Finally, we discuss remedies to these undesirable pores are discussed. The results are validated against the experiments and the sensitivity to laser absorptivity.« less

  13. A higher sink competitiveness of the rooting zone and invertases are involved in dark stimulation of adventitious root formation in Petunia hybrida cuttings.

    PubMed

    Klopotek, Yvonne; Franken, Philipp; Klaering, Hans-Peter; Fischer, Kerstin; Hause, Bettina; Hajirezaei, Mohammad-Reza; Druege, Uwe

    2016-02-01

    The contribution of carbon assimilation and allocation and of invertases to the stimulation of adventitious root formation in response to a dark pre-exposure of petunia cuttings was investigated, considering the rooting zone (stem base) and the shoot apex as competing sinks. Dark exposure had no effect on photosynthesis and dark respiration during the subsequent light period, but promoted dry matter partitioning to the roots. Under darkness, higher activities of cytosolic and vacuolar invertases were maintained in both tissues when compared to cuttings under light. This was partially associated with higher RNA levels of respective genes. However, activity of cell wall invertases and transcript levels of one cell wall invertase isogene increased specifically in the stem base during the first two days after cutting excision under both light and darkness. During five days after excision, RNA accumulation of four invertase genes indicated preferential expression in the stem base compared to the apex. Darkness shifted the balance of expression of one cytosolic and two vacuolar invertase genes towards the stem base. The results indicate that dark exposure before planting enhances the carbon sink competitiveness of the rooting zone and that expression and activity of invertases contribute to the shift in carbon allocation. PMID:26795147

  14. Formation of the seed layers for layer-transfer process silicon solar cells by zone-heating recrystallization of porous silicon structures

    NASA Astrophysics Data System (ADS)

    Lukianov, A.; Murakami, K.; Takazawa, C.; Ihara, M.

    2016-05-01

    Thin-film crystalline silicon is promising for photovoltaic application to reduce the cost of photovoltaic energy. Porous silicon structures have been intensively studied as a seed layer for epitaxial growth of thin Si film and layer-transfer process (LTP). In this article, another approach for LTP has been proposed. The seed layers for epitaxial silicon growth have been formed by zone-heating recrystallization of double-layer por-Si structures. The influence of annealing parameters on porous silicon structures was studied. The transformation of por-Si layer to crystalline Si was observed with the formation of smooth continuous surface with the roughness 0.3 nm, peak-to-valley distance around 3.5 nm, and reduced density of pores. The mechanism of the transformation of por-Si surface due to the action of hydrogen in the passivated pores with preventing surface oxidation was proposed.

  15. Porosity and Organic Carbon Controls on Naturally Reduced Zone (NRZ) Formation Creating Microbial ';Hotspots' for Fe, S, and U Cycling in Subsurface Sediments

    NASA Astrophysics Data System (ADS)

    Jones, M. E.; Janot, N.; Bargar, J.; Fendorf, S. E.

    2013-12-01

    Previous studies have illustrated the importance of Naturally Reduced Zones (NRZs) within saturated sediments for the cycling of metals and redox sensitive contaminants. NRZs can provide a source of reducing equivalents such as reduced organic compounds or hydrogen to stimulate subsurface microbial communities. These NRZ's are typically characterized by low permeability and elevated concentrations of organic carbon and trace metals. However, both the formation of NRZs and their importance to the overall aquifer carbon remineralization is not fully understood. Within NRZs the hydrolysis of particulate organic carbon (POC) and subsequent fermentation of dissolved organic carbon (DOC) to form low molecular weight dissolved organic carbon (LMW-DOC) provides electron donors necessary for the respiration of Fe, S, and in the case of the Rifle aquifer, U. Rates of POC hydrolysis and subsequent fermentation have been poorly constrained and rates in excess and deficit to the rates of subsurface anaerobic respiratory processes have been suggested. In this study, we simulate the development of NRZ sediments in diffusion-limited aggregates to investigate the physical and chemical conditions required for NRZ formation. Effects of sediment porosity and POC loading on Fe, S, and U cycling on molecular and nanoscale are investigated with synchrotron-based Near Edge X-ray Absorption Fine Structure Spectroscopy (NEXAFS). Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Fourier Transform Infrared spectroscopy (FTIR) are used to characterize the transformations in POC and DOC. Sediment aggregates are inoculated with the natural microbial biota from the Rifle aquifer and population dynamics are monitored by 16S RNA analysis. Overall, establishment of low permeability NRZs within the aquifer stimulate microbial respiration beyond the diffusion-limited zones and can limit the transport of U through a contaminated aquifer. However, the long-term stability of

  16. Potential energy surfaces for atomic oxygen reactions: Formation of singlet and triplet biradicals as primary reaction products with unsaturated organic molecules

    NASA Technical Reports Server (NTRS)

    Jaffe, Richard L.

    1987-01-01

    The experimental study of the interaction of atomic oxygen with organic polymer films under LEO conditions has been hampered by the inability to conduct detailed experiments in situ. As a result, studies of the mechanism of oxygen atom reactions have relied on laboratory O-atom sources that do not fully reproduce the orbital environment. For example, it is well established that only ground electronic state O atoms are present at LEO, yet most ground-based sources are known to produce singlet O atoms and molecules and ions in addition to O(3P). Engineers should not rely on such facilities unless it can be demonstrated either that these different O species are inert or that they react in the same fashion as ground state atoms. Ab initio quantum chemical calculations have been aimed at elucidating the biradical intermediates formed during the electrophilic addition of ground and excited-state O atoms to carbon-carbon double bonds in small olefins and aromatic molecules. These biradicals are critical intermediates in any possible insertion, addition and elimination reaction mechanisms. Through these calculations, we will be able to comment on the relative importance of these pathways for O(3P) and O(1D) reactions. The reactions of O atoms with ethylene and benzene are used to illustrate the important features of the mechanisms of atomic oxygen reaction with unsaturated organic compounds and polymeric materials.

  17. Diagnostics of basal conditions - the formation of extensive zones of surface ribs in ice-sheets and streams

    NASA Astrophysics Data System (ADS)

    Hindmarsh, Richard C. A.; Sergienko, Olga V.; Creyts, Timothy T.

    2015-04-01

    Most if not all current predictions of the evolution of ice-streams to changes induced by global change assume static basal conditions. This is a result of current restrictions in the remote sensing of the ice-sheet basal physical environment, which cannot resolve the small-scale phenomena believed to control the basal traction. The search therefore is on for observable structures or features that are the result of the operation of basal processes. Any successful theory of ice-sheet basal processes would need to be able to explain such phenomena associated with or caused by special properties of the basal environment. We present one class of these phenomena, and also present tentative hypotheses as to their formation. Using recent high-resolution observations of the Antarctic and Greenland ice sheets topography, the computed driving stress and the inferred basal traction reveal broad-scale organization in 5-20 km band-like patterns in both quantities. The similarity of patterns on the Greenland and Antarctic ice sheets suggests that the flow of ice sheets is controlled by the same fundamental processes operating at their base, which control ice sheet sliding and are highly variable on relatively short spatial and temporal scales. The formation mechanism for these bands contains information about the operation of the sub-glacial system. There are three possible, non-exclusive causes of these ribs which we examine from a theoretical and evidential point-of-view (i) They are the surface response to similar bands in the basal topography, whose regularity would equally require an explanation in terms of basal processes. (ii) They are translating surface waves in the ice, supported by membrane stress gradients rather than by gradients in the basal resistance. (iii) The ribs are due to the development of a band-like structure in the basal shear stress distribution that is the result of a pattern-forming instability in sub-glacial till and water flow, perhaps related to

  18. In-line coupling of microextractions across polymer inclusion membranes to capillary zone electrophoresis for rapid determination of formate in blood samples.

    PubMed

    Pantůčková, Pavla; Kubáň, Pavel; Boček, Petr

    2015-08-01

    Polymer inclusion membranes (PIMs) have several important features, i.e., PIMs are dry and non-porous membranes, which can be prepared ahead of use and stored without noticeable deterioration in extraction performance. In this contribution, in-line coupling of microextractions across PIMs to a separation method for clinical purposes was demonstrated for the first time. Formate (the major metabolite in methanol poisoning) was determined in undiluted human serum and whole blood by capillary zone electrophoresis (CZE) with simultaneous capacitively coupled contactless conductivity detection (C(4)D) and UV-Vis detection. A purpose-made microextraction device with PIM was coupled to a commercial CZE instrument in order to ensure complete automation of the entire analytical procedure, i.e., of formate extraction, injection, CZE separation and quantification. PIMs for formate extractions consisted of 60% (w/w) cellulose triacetate as base polymer and 40% (w/w) Aliquat™ 336 as anion carrier. The method was characterized by good repeatability of peak areas (≤7.0%) and migration times (≤0.8%) and by good linearity of calibration curves (r(2) = 0.993-0.999). Limits of detection in various matrices ranged from 15 to 54 μM for C(4)D and from 200 to 635 μM for UV-Vis detection and were sufficiently low to clearly distinguish between endogenous and toxic levels of formate in healthy and methanol intoxicated individuals. In addition, PIMs proved that they may act as phase interfaces with excellent long-term stability since once prepared, they retained their extractions properties for, at least, two months of storage. PMID:26320792

  19. Carbanion reactivity, kinetic and equilibrium studies of sigma-adduct formation and elimination in the reactions of 4-nitrobenzofurazan derivatives with nitroalkane anions.

    PubMed

    Asghar, Basim H M; Crampton, Michael R

    2007-05-21

    1H NMR studies are reported of the reactions in [2H(6)]-DMSO of 4-nitrobenzofurazan, 2a, and its 7-chloro- and 7-methoxy-derivatives, 2b and 2c respectively, with anions derived from nitromethane, 3, nitroethane, 4, and 2-nitropropane, 5. The initial reactions result in sigma-adduct formation by carbanion attack at the 5-position of 2a-c and in the case of reaction of 2a with 5 the adduct at the 7-position is also observed. These reactions may be followed by base catalysed elimination of nitrous acid to yield anionic alkene derivatives. Kinetic and equilibrium measurements of these reactions were made spectrophotometrically in methanol. The carbon nucleophilicities of the carbanions decrease in the order 3> 4> 5, as also found in their reactions with benzhydrylium cations, and are much lower than the nucleophilicities of some cyano-substituted carbanions. Comparison with corresponding sigma-adduct forming reactions of 1,3,5-trinitrobenzene, TNB, show that here 2 and TNB have similar electrophilicity, although the value of the intrinsic rate coefficient k(o) = 0.05, for reaction of 2 is rather lower than that, k(o) = 0.20, for the TNB reactions. Literature data suggest that for reaction with a variety of nucleophiles 2 and TNB show similar electrophilicities. Measurements of the rates of elimination of nitrous acid from some 5-adducts in methanol catalysed by methoxide ions are reported. Values of rate constants may be influenced both by steric requirements at the reaction centre and by the electronic effects of the 7-substituent. PMID:17571196

  20. Using U-series isotopes to quantify regolith formation and chemical weathering rates along a climosequence associated with the Susquehanna Shale Hills Critical Zone Observatory

    NASA Astrophysics Data System (ADS)

    Ma, L.; Chabaux, F. J.; Dere, A. L.; White, T.; Jin, L.; Brantley, S. L.

    2012-12-01

    Regolith formation and chemical weathering are important Critical Zone processes and are responsible for soil development. Despite their fundamental importance, we still lack effective tools to quantify these processes. U-series isotopes offer a powerful geochronometer to quantify regolith production rates and weathering duration. This is largely due to improvements in analytical methods and mathematical approaches made over the last decade in measuring U-series isotopes and interpreting their fractionation during chemical weathering. Here, we present a systematic study of U-series isotopes (238U, 234U and 230Th) in shale-derived soils from five small watersheds in the eastern USA to understand the rates of regolith formation as a function of climate. The selected watersheds in Pennsylvania, Virginia, Tennessee, Alabama, and Puerto Rico are part of the shale transect established as part of the Susquehanna Shale Hills Critical Zone Observatory. We first measured U-series isotopes in six regolith profiles from two planar hill-slopes (north vs. south) within the Shale Hills CZO in central PA to evaluate the role of aspect on regolith formation in the small watershed. All regolith samples display significant U-series disequilibrium. These U-series disequilibrium values are explained by two processes acting on U-series isotopes during weathering: a loss of 234U, 238U, and 230Th during water-rock interactions and a gain from circulating soil water and/or downslope particle transport. Regolith production rates and weathering durations were calculated with a U-series isotope mass balance model. On the southern (shaded) slope, regolith production rates decrease systematically with increasing soil thickness and distance from the ridge: from ~44.5 m/Myr at the ridge top to ~15.0 m/Myr at the valley floor. Durations of chemical weathering within these profiles range from 6.7 kyr to 44.7 kyr, increasing from the ridge to the valley floor. The regolith profiles on the northern

  1. Meteoric water-rock interaction and clay-gouge formation during higher temperature brittle faulting on the Silltal-Brenner Fault Zone, Eastern Alps (Austria)

    NASA Astrophysics Data System (ADS)

    Mancktelow, Neil; Zwingmann, Horst; Campani, Marion; Fügenschuh, Bernhard; Mulch, Andreas

    2015-04-01

    The Silltal Fault is the northern brittle continuation of the Brenner Fault Zone, with a normal, down-to-west sense of movement. It is marked by a narrow zone of cataclasis and, in three sampled locations, clay-rich fault gouges. The clay mineral composition of these gouges is dominated by higher temperature 2M1 polytype illite/muscovite, with no 1M/1Md illite or mixed layer illite/smectite detected. Smectite is limited to the northern samples from the Stephansbrücke location, whereas chlorite is present in all samples. New growth of 2M1 polytype illite in the finest size fractions indicates temperatures > 200-250° C and therefore fault gouge development at depths and temperatures close to the ductile-brittle transition in quartz rich rocks (~280-300° C). Hydrogen stable isotope (δD) analyses show that gouge formation was associated with the influx of meteoric water, which was strongly focused within the fault zone itself, without significant interchange with the adjacent footwall and hanging wall rocks. K-Ar ages from the different sample grain size fractions (< 0.1 to 6-10 μm and 'whole rock gouge') show a wide spread, from ca. 115 to 12 Ma, with ages consistently decreasing with grain size. Although the ranges overlap, ages from the northern Stephansbrücke samples are generally older (115-36 Ma) than those from the south near Matrei (55-12 Ma), possibly reflecting increasing regional metamorphic temperatures to the south. The well-defined linear relationship between apparent age and hydrogen stable isotope (δD) values establishes a direct correlation between rejuvenation of the K-Ar system and increased interaction with meteoric water. The dependence of both apparent age and δD on grain size also indicates that radiogenic and stable isotope exchange was controlled by grain size, reflecting new 2M1 illite growth, mechanical grinding of protolith muscovite during cataclastic faulting, or both. The results demonstrate the advantages of combining radiogenic

  2. Repeated occurrences of methanogenic zones, diagenetic dolomite formation and linked silicate alteration in southern Bering Sea sediments (Bowers Ridge, IODP Exp. 323 Site U1341)

    NASA Astrophysics Data System (ADS)

    Wehrmann, L. M.; Ockert, C.; Mix, A. C.; Gussone, N.; Teichert, B. M. A.; Meister, P.

    2016-03-01

    Diagenetic precipitates, such as dolomite, and the chemistry of residual deeply buried porewater often represent the only traces of past biogeochemical activity in marine sediments. A 600 m thick sedimentary section, recently drilled at Integrated Ocean Drilling Program (IODP) Site U1341 on Bowers Ridge (southern Bering Sea), provides insight into such a 4.3 Ma old paleo-diagenetic archive. Hard-lithified calcite-dolomite layers, and laminae of disseminated carbonate, were recovered in diatom-rich sediments over a depth range of 400 m. Carbon isotope values of the diagenetic carbonates between -16.6 and -14.4‰ (VPDB) and strontium isotope ratios of dolomites close to past seawater values suggest carbonate precipitation induced by the production of dissolved inorganic carbon (DIC) during elevated rates of organic carbon mineralization, primarily via sulfate reduction, at shallow sediment depth below the paleo-seafloor. Diagenetic carbonates at 280-440 m below seafloor were likely also produced by the intermittent onset of sulfate reduction coupled to the anaerobic oxidation of methane (AOM) at sulfate-methane transition zones (SMTZ). These microbially mediated processes do not occur in the sediment at this site at present but were likely connected to the presence of a methanogenic zone at 2.58-2.51 Ma. A minimum in sulfate concentrations in modern porewaters and low sedimentary Ba/Al ratios resulting from former sulfate depletion are reminiscent of the presence of this large methanogenic zone. The minimum in sulfate concentrations is reflected in a minimum in magnesium concentrations, less radiogenic strontium and isotopically light calcium in the porewater. It is proposed that magnesium was removed from the porewater during carbonate precipitation and volcanic ash alteration which occurred in the former methanogenic zone and also released strontium with a less radiogenic isotope ratio and isotopically light calcium into the porewater. The isotopic composition of

  3. How spatial variations of chalk groundwater geochemistry are related to superficial formations and infiltration processes of unsaturated zone (quarry of Saint Martin le Noeud, France)

    NASA Astrophysics Data System (ADS)

    Barhoum, Sarah; Valdès-Lao, Danièle; Guérin, Roger; Gombert, Philippe

    2013-04-01

    Chalk is complex because of its dual porosity and because of superficial layers more or less thick and more or less permeable. Furthermore there is few knowledge in understanding of groundwater infiltration and dissolution processes in the chalk unsaturated zone (UZ). The role of superficial formations has to be studied especially. The experimental site is an ancient underground quarry of chalk which extends over 1200 m long and 150 m wide (30 m depth) in Saint Martin le Noeud, south of Beauvais, France. This quarry is particularly interesting to study infiltration and dissolution processes indeed this site allows to access to the interface between the unsaturated zone and the saturated zone. Water percolates from the top of the quarry more or less depending on the season. Water table outcrops in the cave and makes about 20 underground lakes. Above the quarry chalk is covered clay-with-flints (CWF) and loess, in surface there are cultivated crops fields. On the first year of the study, physicochemical parameters: temperature, depth, pH, conductivity were recorded in seven lakes with high frequency (every hour). During the same period we sampled the 20 lakes water every month to measure major ions. During this sampling period, percolation was not sufficient to collect percolated water. Results of underground GPS, electric resistivity tomography and observations of three borehole showed that thickness unsaturated zone and that the thicknesses of the superficial formations vary a lot spatially. Three interesting points (separated by less than 1 km) are presented: the above the Pedro lake (25 m of UZ, a few cm of CWF), above the Stalactites lake (30 m of UZ, more than 2.40 m of CWF); above the Blue lake (35 m depth, 60 cm of CWF). First results of chemistry showed that the temporal variation is very low during the first year but there spatial variation is very important at quarry scale. The geochemistry of the lakes are very different: HCO3- varies from 100 to 250mg

  4. Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief