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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. FLUID EVOLUTION AND MINERAL REACTIONS DURING SHEAR ZONE FORMATION AT NUSFJORD, LOFOTEN, NORWAY (Invited)

    NASA Astrophysics Data System (ADS)

    Kullerud, K.

    2009-12-01

    At Nusfjord in Lofoten, Norway, three 0.3 - 3 m thick shear zones occur in a gabbro-anorthosite. During deformation, the shear zones were infiltrated by a hydrous fluid enriched in Cl. In the central parts of the shear zones, fluid-rock interaction resulted in complete break-down of the primary mafic silicates. Complete hydration of these minerals to Cl-free amphibole and biotite suggests that the hydrous fluid was present in excess during deformation in these parts of the shear zones. Along the margins of the shear zones, however, the igneous mafic silicates (Cpx, Bt, Opx) were only partly overgrown by hydrous minerals. Here, Cl-enriched minerals (Amph, Bt, Scp, Ap) can be observed. Amphibole shows compositions covering the range 0.1 - 4.0 wt % Cl within single thin sections. Mineral textures and extreme compositional variations of the Cl-bearing minerals indicate large chemical gradients of the fluid phase. Relics of primary mafic silicates and compositionally zoned reaction coronas around primary mafic silicates suggest that the free fluid was totally consumed before the alteration of the primary phases were completed. The extreme variations in the Cl-content of amphibole are inferred to monitor a gradual desiccation of the Cl-bearing grain-boundary fluid during fluid-mineral reactions accordingly: 1) The first amphibole that formed during the reactions principally extracted water from the fluid, resulting in a slight increase in the Cl content of the fluid. 2) Continued amphibole-forming reactions resulted in gradual consumption of the free fluid phase, principally by extracting water from the fluid, resulting in an increase in its Cl-content. Higher Cl-content of the fluid resulted in higher Cl-content of the equilibrium amphibole. 3) The most Cl-enriched amphibole (4 wt % Cl) formed in equilibrium with the last volumes of the grain-boundary fluid, which had evolved to a highly saline solution. Mineral reactions within a 1-2 thick zone of the host rock along

  3. Secondary Reaction Zone Formations in coated Ni-base Single Crystal Superalloys

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Rae, C. M. F.

    2009-05-01

    Ruthenium (Ru) has been added to the latest 4th Generation Ni-base superalloys to improve phase stability and modify creep life. Various coatings are routinely applied to these advanced alloys to protect the turbine blade at elevated temperature, however, this creates several problems such as the precipitation of brittle Topologically Close-Packed (TCP) phases and the formation of Secondary Reaction Zones (SRZ). The SRZ forms under the plat-aluminized coating of turbine blades and consists of γ, γ and TCP phases growing into substrate by the migration of high-angle grain boundaries. Surface residual stress and chemical super-saturation of alloying elements are associated to SRZ formation. In the thin sections of high-pressure turbine blades this is critical in determining blade performance and longevity. It is essential to know how Ru additions affect coating and SRZ morphologies during exposure. In this study, we focus on the effects of three variables on the SRZ formation: Ru concentration, alloy composition in Ru-containing alloys and surface finish. A series of Platinum-Aluminised superalloys containing 2-5wt% Ru and having various surface finishes was studied after isothermal exposure at 1100°C for up to 500h. The alloys were classified into two groups by their distinctive SRZ morphology. At the lowest Ru levels sporadic formation of SRZ was observed, whilst a continuous SRZ was formed in the higher Ru alloys. EBSD analysis revealed that the latter group have a higher nucleation rate of individual SRZ grains and also showed more rapid SRZ growth. The precipitation of TCPs in the substrate also inhibited the growth of the SRZ towards the end of the exposure further reducing the penetration of the SRZ into the substrate. It is concluded that Ru-additions to Ni-base superalloys are effective in impeding TCP phase formation in the substrate, but increase both the extent and the rate of SRZ formation beneath coating.

  4. Formation of Secondary Reaction Zones in Diffusion Aluminide-Coated Ni-Base Single-Crystal Superalloys Containing Ruthenium

    NASA Astrophysics Data System (ADS)

    Das, Dipak K.; Murphy, Kenneth S.; Ma, Shuwei; Pollock, Tresa M.

    2008-07-01

    The formation of secondary reaction zones (SRZs) beneath aluminide coatings in several Ru-bearing single-crystal Ni-base superalloys has been investigated. The presence of significant amounts of Ru in the superalloys did not prevent the formation of the secondary reaction zone. However, the Ru content of the alloys affected the type of refractory element-rich phase formed during the transformation. As the Ru content increased, the phase involved in the transformation shifted from the orthorhombic P to the β-RuAl phase. A differential tendency to SRZ formation was observed between the dendritic and interdendritic regions of the alloys. Significant growth of the SRZ was also observed during the high-temperature oxidation exposure of the coated alloys. The effects of the alloying elements on SRZ formation are discussed.

  5. 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.

  6. 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.

  7. 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).

  8. 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.

  9. 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

  10. 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

  11. 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.

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

    DOE PAGES

    Hooper, R. J.; Davis, C. G.; Johns, P. M.; ...

    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

  13. The formation of grounding zone wedges

    NASA Astrophysics Data System (ADS)

    Kowal, Katarzyna; Worster, Grae

    2016-11-01

    Ice sheets are generally lubricated by a layer of sub-glacial sediment, or till, which plays a central role in determining their large-scale dynamics. Sub-glacial till has been found to accumulate into distinctive sedimentary wedges at ice-sheet grounding zones, separating floating ice shelves from grounded ice sheets. These grounding-zone wedges have important implications for stabilizing ice sheets against grounding-zone retreat in response to rising sea levels. We develop a theoretical model of wedge formation in which we treat both ice and till as viscous fluids spreading under gravity into an inviscid ocean and present a fluid-mechanical explanation of the formation of these wedges in terms of the jump in hydrostatic loading and unloading of till across the grounding zone. We also conduct a series of fluid-mechanical experiments in a confined setting in which we find that the underlying layer of less viscous fluid accumulates spontaneously in a similar wedge-shaped region at the experimental grounding line. We also extend our theory to more natural, unconfined settings in two dynamical regimes in which the overlying ice is resisted dominantly either by vertical shear or by extensional stresses and compare our findings with available geophysical data. Currently at Northwestern University.

  14. Reaction zone structure in supracompressed detonating explosives

    SciTech Connect

    Green, L.G.; Tarver, C.M.; Erskine, D.J.

    1989-08-18

    Nanosecond time resolved particle velocity histories of supracompressed detonation waves in TNT-, TATB-, and HMX-based explosives are measured using a VISAR laser velocimeter and calculated using the ignition and growth reactive flow hydrodynamic computer code model. The Zeldovich-von Neumann-Doering (ZND) detonation wave structure is observed at pressures more than twice the self-sustaining detonation wave pressure. TNT and TATB exhibited a fast reaction which liberates approximately 80% of the total available exothermicity within 50 ns, followed by a slower reaction which lasts another 100--200 ns. These reaction rates are not strongly dependent on the initial shock pressure. The slower reaction is attributed to diffusion controlled solid carbon coagulation. The ignition and growth model using a ZND type model with a fast reaction preceding a slower reaction to the fully reacted product state accurately calculates the VISAR experimental data for TNT, LX-17, PBX 9404 and RX-26-AF. 21 refs., 15 figs., 3 tabs.

  15. 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.

  16. Regular satellite formation and evolution in a dead zone

    NASA Astrophysics Data System (ADS)

    Chen, Cheng; Martin, Rebecca G.

    2017-01-01

    The dead zone in a circumplanetary disk is a non-turbulent region at the disk midplane that is an ideal location for regular satellite formation. The lower viscosity in the dead zone allows small objects to accrete and grow. We model the evolution of a circumplanetary disk with a dead zone for a range of disk and dead zone parameters. We investigate how these affect the formation and subsequent evolution of regular satellites that form in the disk.

  17. Varying heating in dawsonite zones in hydrocarbon containing formations

    SciTech Connect

    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.

  18. 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)

  19. 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.

  20. 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.

  1. 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…

  2. Elementary reaction modeling of solid oxide electrolysis cells: Main zones for heterogeneous chemical/electrochemical reactions

    NASA Astrophysics Data System (ADS)

    Li, Wenying; Shi, Yixiang; Luo, Yu; Cai, Ningsheng

    2015-01-01

    A theoretical model of solid oxide electrolysis cells considering the heterogeneous elementary reactions, electrochemical reactions and the transport process of mass and charge is applied to study the relative performance of H2O electrolysis, CO2 electrolysis and CO2/H2O co-electrolysis and the competitive behavior of heterogeneous chemical and electrochemical reactions. In cathode, heterogeneous chemical reactions exist near the outside surface and the electrochemical reactions occur near the electrolyte. According to the mathematical analysis, the mass transfer flux D ∇c determines the main zone size of heterogeneous chemical reactions, while the charge transfer flux σ ∇V determines the other one. When the zone size of heterogeneous chemistry is enlarged, more CO2 could react through heterogeneous chemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to H2O electrolysis. Meanwhile, when the zone size of electrochemistry is enlarged, more CO2 could react through electrochemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to CO2 electrolysis. The relative polarization curves, the ratio of CO2 participating in electrolysis and heterogeneous chemical reactions, the mass and charge transfer flux and heterogeneous chemical/electrochemical reaction main zones are simulated to study the effects of cathode material characteristics (porosity, particle diameter and ionic conductivity) and operating conditions (gas composition and temperature).

  3. Reaction kinetics of fuel formation for in-situ combustion

    SciTech Connect

    Abu-Khamsin, S.; Ramey, H.J. Jr.; Pettit, P.; Brigham, W.E.

    1985-07-01

    In-situ combustion is receiving new interest as a viable alternative to the other thermal methods of heavy crude oil recovery. In this method, thermal energy is generated in-situ by creating an oil combustion zone that is driven through the reservoir by continuous air injection. While the various oil oxidation reactions have been adequately studied and modeled, little information is available regarding the fuel formation process that takes place ahead of the combustion zone. The goal of this study was to investigate the reactions that contribute to this process and obtain generalized kinetic equations for them. An experimental apparatus was built wherein a small sample of an oil/sand mixture can be pyrolyzed at a constant rate of heating, to temperatures normally encountered in combustion field applications, while nitrogen is continuously sweeping the sample. The effect on fuel formation of pressure, rate of heating, porous medium composition, and type of oil were investigated in an experimental program totaling 12 runs. Data from previously made oxidation experiments were also used. General conclusions reached in this study are: (1) the fuel is formed as a result of two successive cracking reactions that the oil undergoes at temperatures above 550/sup 0/F; distillation of crude oil at temperatures below 550/sup 0/F plays an important role in shaping the nature and extent of the cracking reactions; (3) the operating pressure and rate of heating affect the fuel formation process only through the influences exerted on distillation; (4) clay minerals have a catalytic effect on the cracking reactions, especially on coking; and (5) the asphaltene fraction of a crude oil is a parameter which correlates with the fuel content of that oil. 51 refs., 73 figs., 21 tabs.

  4. Particle velocity measurements of the reaction zone in nitromethane

    SciTech Connect

    Sheffield, S. A.; Engelke, R. P.; Alcon, R. R.; Gustavsen, R. L.; Robbins, D. L.; Stahl, D. B.; Stacy, H. L.; Whitehead, M.

    2002-01-01

    The detonation reaction-zone length in neat, deuterated, and chemically sensitized nitromethane (NM) has been measured by using several different laser-based velocity interferometry systems. The experiments involved measuring the particle velocity history at a NM/PMMA (polymethylmethacrylate) window interface during the time a detonation in the NM interacted with the interface. Initially, Fabry-Perot interferometry was used, but, because of low time resolution (>5 ns), several different configurations of VISAR interferometry were subsequently used. Early work was done with VISARs with a time resolution of about 3 ns. By making changes to the recording system, we were able to improve this to {approx}1 ns. Profiles measured at the NM/PMMA interface agree with the ZND theory, in that a spike ({approx}2.45 mm/{micro}s) is measured that is consistent with an extrapolated reactant NM Hugoniot matched to the PMMA window. The spike is rather sharp, followed by a rapid drop in particle velocity over a time of 5 to 10 ns; this is evidence of early fast reactions. Over about 50 ns, a much slower particle velocity decrease occurs to the assumed CJ condition - indicating a total reaction zone length of {approx}300 {micro}m. When the NM is chemically changed, such as replacing the hydrogen atoms with deuterium or chemically sensitizing with a base, some changes are observed in the early part of the reaction zone.

  5. 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.

  6. Molecular Dynamics Analysis of a Liquid Explosive Reaction Zone

    NASA Astrophysics Data System (ADS)

    Soulard, L.; Crouzet, B.

    2006-07-01

    We present an analysis of the reaction zone of a stationary planar detonation by a equilibrium molecular dynamics method (EMD). We particularly focus on the influence of chemical characteristics such as the reactions reversibility and endothermicity. First, equilibrium and unreacted Hugoniot of the reactive system are calculated by EMD. These results are then used to predict the detonation characteristics such as the thermodynamic properties of ZND spike and the sonic point. We observe in particular the influence of the preliminary endothermic phase on the detonation velocity and its stability. The comparison between these predictions and non equilibrium molecular dynamics calculations validate the EMD method.

  7. Seismic probing of hydration and dehydration reactions in subduction zones

    NASA Astrophysics Data System (ADS)

    Rondenay, Stéphane; McGary, R. Shane; Halpaap, Felix; Goes, Saskia; Perrin, Alexander; Wang, Hongliang; Huismans, Ritske; Ottemöller, Lars

    2017-04-01

    Over the past decade, high-resolution images based on teleseismic scattered waves have given us new insight into the distribution and movement of water in subduction zones. In particular, these images have shown us where the subducted crust loses the bulk of its water through eclogitization and where the mantle wedge becomes hydrated via serpentinization. The first images provided adequate constraints to infer where these processes occur for uniformly hydrated/dehydrated components of the system. However, we know that this assumption of uniformity does not really apply owing to petrological evidence that prograde and retrograde metamorphic reactions do not proceed uniformly across the subducted crust or mantle wedge. Here, we expand on previous work by (i) comparing high-resolution images from a catalogue that now samples a wide range of subduction zones, and (ii) jointly interpreting these high-resolution images with results from complementary seismic/geodynamic/petrological modelling. Our goal is to generate a set of new models that can help us better constrain the variable levels of hydration within the subducted slab and mantle wedge, and to use these models to better understand how fluid transfer between the various components of the system relates to seismicity. We illustrate these concepts with examples from the Cascadia subduction zone, where we find strong evidence for a layer of metastable gabbro in the lower portion of the subducted crust, and the Western Hellenic subduction zone, where the distribution of intraslab seismicity seems indicative of variable hydration/dehydration regimes along strike.

  8. 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.

  9. Molecular dynamics analysis of a liquid explosive reaction zone

    NASA Astrophysics Data System (ADS)

    Soulard, Laurent

    2005-07-01

    We present in this work a detailed analysis by molecular dynamics of the reaction zone of a stationary planar detonation. In particular, we look at the influence of chemical characteristics such as the reactions reversibility and endothermicity. So, equilibrium and frozen Hugoniot of the reactive system are calculated by a specific molecular dynamics method. These results can be used to a predict the detonation characteristics such as the thermodynamic properties of ZND spike and the CJ point. We observe in particular the influence of the preliminary endothermic phase on the detonation velocity and its stability. The comparisons between these predictions and non equilibrium molecular dynamics results confirm the results of this first theoretical part. In a second step, the main hypotheses of a ZND model are extracted from the MD simulations (mainly the formalism of the reactive EOS in the reaction zone). The parameters of the corresponding model are then fitted on MD results. The final step is the implementation of the model in an hydrodynamic code. Direct comparisons between molecular dynamics simulations and hydrodynamics calculations for various 1D and 2D (in the hydrodynamics sens) configurations are presented.

  10. 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.

  11. Reaction zone structure of weak underdriven oblique detonations

    NASA Astrophysics Data System (ADS)

    Powers, Joseph M.; Gonthier, Keith A.

    1992-01-01

    Steady weak underdriven oblique detonations consisting of a lead shock attached to a solid wedge followed by a resolved reaction zone structure are admitted as solutions to the reactive Euler equations for eigenvalue shock wave angles. This is demonstrated for a fluid which is taken to be an inviscid, calorically perfect ideal gas which undergoes a two-step irreversible reaction with the first-step exothermic and the second-step endothermic. These solutions represent two-dimensional extensions of one-dimensional weak detonations. In addition, this model admits solutions to the other two classes of solutions identified by a Rankine-Hugoniot analysis, namely weak overdriven and strong waves. Chapman-Jouguet waves, however, are not admitted. These results contrast those for a corresponding one-step model which, for detonations with a lead shock, only admits weak overdriven, strong, and Chapman-Jouguet solutions.

  12. Reaction enhanced channelised fluid-flux along mid- crustal shear zone: An example from Mesoproterozoic Phulad Shear Zone, Rajasthan, India

    NASA Astrophysics Data System (ADS)

    Chatterjee, Sadhana M.; Choudhury, Manideepa Roy; Das, Subhrajyoti

    2016-10-01

    Fluid infiltration at great depth during regional metamorphism plays a major role in mass transport and is responsible for significant rheological changes in the rock. Calc-silicate rocks of the Kajalbas area of Delhi Fold Belt, Rajasthan, are characterised by foliation parallel alternate bands of amphibole-rich and clinopyroxene-plagioclase feldspar-rich layers of varying thicknesses (mm to decimetre thick). Textural relation suggests that the amphibole grains formed from clinopyroxene and plagioclase in the late phase of regional deformation. Algebraic analysis of the reaction textures and mineral compositions was performed with the computer program C-Space to obtain the balanced chemical reactions that led to the formation of amphibole-rich bands. The computed balanced reaction is 70.74 Clinopyroxene + 27.23 Plagioclase + 22.018 H2O + 5.51 K++ 1.00 Mg2++ 27.15 Fe2+ = 22.02 Amphibole + 67.86 SiO2 aqueous + 36.42 Ca2++ 8.98 Na+. The constructed reaction suggests that aqueous fluid permeated the calc-silicate rock along mm to decimetre thick channels, metasomatized the clinopyroxene-plagioclase bearing rocks to form the amphibole-rich layers. The regional deformation presumably created the fluid channels thereby allowing the metasomatic fluid to enter the rock system. The above reaction has large negative volume change for solid phases indicating reaction-induced permeability. Thermodynamic calculations suggest that the fluid-rock interaction occurred at 665 ±05∘C and 6.6 ±0.25 kbar (corresponding to ˜20 km depth). Textural modeling integrating the textural features and balanced chemical reaction of the calc-silicate rocks of Mesoproterozoic Phulad Shear Zone thus indicate that extremely channelled fluid flow was reaction enhanced and caused major change in the rock rheology.

  13. Reaction-induced grain boundary cracking and anisotropic fluid flow during prograde devolatilization reactions within subduction zones

    NASA Astrophysics Data System (ADS)

    Okamoto, Atsushi; Shimizu, Hiroyuki; Fukuda, Jun-ichi; Muto, Jun; Okudaira, Takamoto

    2017-09-01

    Devolatilization reactions during prograde metamorphism are a key control on the fluid distribution within subduction zones. Garnets in Mn-rich quartz schist within the Sanbagawa metamorphic belt of Japan are characterized by skeletal structures containing abundant quartz inclusions. Each quartz inclusion was angular-shaped, and showed random crystallographic orientations, suggesting that these quartz inclusions were trapped via grain boundary cracking during garnet growth. Such skeletal garnet within the quartz schist formed related to decarbonation reactions with a positive total volume change (Δ V t > 0), whereas the euhedral garnet within the pelitic schists formed as a result of dehydration reaction with negative Δ V t values. Coupled hydrological-chemical-mechanical processes during metamorphic devolatilization reactions were investigated by a distinct element method (DEM) numerical simulation on a foliated rock that contained reactive minerals and non-reactive matrix minerals. Negative Δ V t reactions cause a decrease in fluid pressure and do not produce fractures within the matrix. In contrast, a fluid pressure increase by positive Δ V t reactions results in hydrofracturing of the matrix. This fracturing preferentially occurs along grain boundaries and causes episodic fluid pulses associated with the development of the fracture network. The precipitation of garnet within grain boundary fractures could explain the formation of the skeletal garnet. Our DEM model also suggests a strong influence of reaction-induced fracturing on anisotropic fluid flow, meaning that dominant fluid flow directions could easily change in response to changes in stress configuration and the magnitude of differential stress during prograde metamorphism within a subduction zone.

  14. Spatiotemporal evolution of dehydration reactions in subduction zones (Invited)

    NASA Astrophysics Data System (ADS)

    Padron-Navarta, J.

    2013-12-01

    Large-scale deep water cycling takes place through subduction zones in the Earth, making our planet unique in the solar system. This idiosyncrasy is the result of a precise but unknown balance between in-gassing and out-gassing fluxes of volatiles. Water is incorporated into hydrous minerals during seafloor alteration of the oceanic lithosphere. The cycling of volatiles is triggered by dehydration of these minerals that release fluids from the subducting slab to the mantle wedge and eventually to the crust or to the deep mantle. Whereas the loci of such reactions are reasonably well established, the mechanisms of fluid migration during dehydration reactions are still barely known. One of the challenges is that dehydration reactions are dynamic features evolving in time and space. Experimental data on low-temperature dehydration reactions (i.e. gypsum) and numerical models applied to middle-crust conditions point to a complex spatiotemporal evolution of the dehydration process. The extrapolation of these inferences to subduction settings has not yet been explored but it is essential to understand the dynamism of these settings. Here I propose an alternative approach to tackle this problem through the textural study of high-pressure terrains that experienced dehydration reactions. Spatiotemporal evolution of dehydration reactions should be recorded during mineral nucleation and growth through variations in time and space of the reaction rate. Insights on the fluid migration mechanism could be inferred therefore by noting changes in the texture of prograde assemblages. The dehydration of antigorite in serpentinite is a perfect candidate to test this approach as it releases a significant amount of fluid and produces a concomitant porosity. Unusual alternation of equilibrium and disequilibrium textures observed in Cerro del Almirez (Betic Cordillera, S Spain)[1, 2] attest for a complex fluid migration pattern for one of the most relevant reactions in subduction zones

  15. 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.

  16. 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

  17. Fluid Flow, Reactions and Exhumation of Mantle Peridotite Along a Serpentinite Fault Zone.

    NASA Astrophysics Data System (ADS)

    Tulley, C. J.; Smith, S. A. F.; Scott, J.; Tarling, M. S.; le Roux, P. J.

    2016-12-01

    The last phase of exhumation of a > 1000 km long belt of Permian mantle (Dun Mountain Ophiolite Belt) in New Zealand was achieved by movements along the Livingstone Fault. At Mt Raddle and Mt Richards in the Olivine Range, near-pristine mantle harzburgite shows a complete transition through to the serpentinite melange of the Livingstone Fault, which juxtaposes the ultramafics against quartzofeldspathic crust. A talc-tremolite-diopside reaction zone developed at the serpentinite-crustal contact, with diopside overgrowing tremolite. We suspect that the initial formation of frictionally weak talc helped to localise deformation within the reaction zone. The hydration of peridotite is intimately linked to fluid flow along the Livingstone Fault, since water-bearing phases increase with proximity to the fault melange. The transformation of harzburgite to serpentinite is marked by serpentinisation of clinopyroxene and olivine, development of chromite from Cr spinel (Cr# increases from 45 to 97) and overgrowths of secondary olivine ( Fo82-85) around orthopyroxene. As the melange is approached, magnetite forms at the expense of Fe-bearing mantle minerals. The replacement of primary spinel released Al and Mg, which now forms nano-scale intergrowths of chlorite and lizardite. The scaly serpentinite melange is up to 80 m wide at Mt Raddle and contains pods of massive serpentinite, some with remnant peridotite texture. At Mt Richards, 2 km along strike, the melange narrows and fresh peridotite is exposed within 20 m of the quartzofeldspathic rocks. This change in fault zone structure implies that fluid ingress into the ultramafics was highly variable during the exhumation process. The Livingstone Fault may provide insights in to the decoupling of crust and mantle above a subduction zone. The infiltration of fluid along the fault interface acted as a lubricant, driving hydration reactions and enabling adjacent fresh mantle peridotite to be brought towards the Earth's surface.

  18. Mechanisms of myrmekite formation: case study from the Weinsberg granite, Moldanubian zone, Upper Austria

    NASA Astrophysics Data System (ADS)

    Abart, Rainer; Heuser, David; Habler, Gerlinde

    2014-11-01

    Myrmekites have attracted the attention of petrographers over more than a century, and several genetic models have been proposed. We report on myrmekites from the Weinsberg granite of the Moldanubian zone of Upper Austria. Based on petrographic evidence, fluid-mediated replacement of alkali feldspar by myrmekite during the sub-solidus evolution of the granite is inferred. The replacement was metasomatic on the scale of the myrmekite domains requiring addition of sodium and calcium and removal of potassium from the reaction site. In contrast, silica and aluminum were conserved across the reaction front. Myrmekite formation appears to have been synchronous with and related to the hydration of orthopyroxene and concomitant replacement of primary magmatic plagioclase by biotite at around 500 °C. The evolution of the myrmekite microstructure and a peculiar composition zoning of the plagioclase constituting the myrmekite matrix is qualitatively explained by a model for discontinuous precipitation, which accounts for chemical segregation by diffusion within the reaction front and the propagation of the reaction front with finite mobility as potentially rate limiting processes. Constraints on the underlying reaction rates are derived from the preserved microstructure and chemical pattern. Crystal orientation imaging by electron backscatter diffraction reveals grain-internal deformation, which is primarily concentrated in the quartz and less pronounced in the plagioclase matrix of the myrmekite. This is interpreted as a growth feature related to different transformation strain at the segments of the myrmekite reaction front, where quartz and plagioclase are formed.

  19. Dynamics of formation of the Exclusion Zone near hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    De Ninno, Antonella

    2017-01-01

    EZ water is unable to host solutes, what provides the root of the name Exclusion Zone, and its formation law points towards a diffusive process. These peculiarities have attracted the interest of scientists because it challenges all the theories which have tried to describe the structure of liquid water. The mixture of H-bond stable and H-bond distorted structures envisaged by very recent experimental findings, cannot account for the long-lived hexagonal configuration observed near the Nafion surface. A theoretical account for the phenomenology of H-bond is provided which looks able to explain many among the most striking feature of this water.

  20. Relativistic nucleus-nucleus collisions: Zone of reactions and space-time structure of fireball

    SciTech Connect

    Anchishkin, D.; Muskeyev, A.; Yezhov, S.

    2010-03-15

    A zone of reactions is determined and then exploited as a tool in studying the space-time structure of an interacting system formed in a collision of relativistic nuclei. The time dependence of the reaction rates integrated over spatial coordinates is also considered. Evaluations are made with the help of the microscopic transport model UrQMD. The relation of the boundaries of different zones of reactions and the hypersurfaces of sharp chemical and kinetic freeze-outs is discussed.

  1. 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

  2. Diffusion layer formation drives zone migration in travelling wave electrophoresis.

    PubMed

    Booth, William Albert; Edwards, Boyd; Jo, Kyoo; Timperman, Aaron; Schiffbauer, Jarrod

    2017-04-04

    COMSOL finite element modeling software is used to simulate 2D traveling-wave electrophoresis for microfluidic separations and sample concentration. A four-phase AC potential is applied to a periodic interdigitated four-electrode array to produce a longitudinal electric wave that travels through the channel. Charged particles are carried along with the electric wave or left behind, depending on their mobilities. A simplified model of asymmetric electrode reactions resolves the issue of electric double layer shielding at the electrodes. Selective reactions allow for the formation of diffusion layers of charged particles which follow the traveling electric wave. These diffusion layers determine the transport of charged species through the system. Our model reproduces experimental separations of charged species based on mobility. With easy control over the frequency and direction, one may employ this method for concentrating and/or separating charged particles.

  3. A simplified reaction mechanism for soot formation in nonpremixed flames

    SciTech Connect

    Leung, K.M.; Lindstedt, R.P. ); Jones, W.P. )

    1991-12-01

    The present article outlines a simplified reaction mechanism for the formation, growth, and combustion of soot particles in laminar nonpremixed flames. The model can be combined with detailed chemistry descriptions for the gas phase, as in the present case, or with reduced chemical reaction mechanisms. The reaction mechanism involves nucleation, surface growth, particle coagulation, and combustion steps. The model outlined has been created with the intention of being applicable to the prediction of turbulent flames via different approaches. The soot nucleation and surface growth reactions are linked to the gas phase by presuming that pyrolysis products, in the present case acetylene, and not the fuel itself, are of primary importance in the soot formation process. The deduced reaction mechanism is applied to counterflow ethylene and propane flames burning with a range of oxygen-enriched and depleted air streams. The results obtained show excellent qualitative and quantitative agreement with measured data for soot volume fraction, particle growth, and number density.

  4. Modeling of formation of intraplate partial melting zones

    NASA Astrophysics Data System (ADS)

    Perepechko, Y. V.; Sorokin, K. E.

    2010-12-01

    This study suggests the mathematical model of dynamics of partial melting in lithosphere causing formation of magmatic systems. The intraplate magmatic systems can be formed at achievement of required thermodynamic conditions, which can be developed due to the following mechanisms: contact heating; decompression melting at mantle matter penetration into lithosphere; and heating by filtering mantle melts and fluids in the weakened lithosphere zones above the asthenospheric structure related to a hotspot. The most efficient mechanism from the point of time and heating degree is the latter one. It is heating of lithosphere matter by mantle melts and fluids, which is especially important for development of melting sites in these systems. At formation of intraplate magmatic systems the fluid is filtered in a porous medium, porous matrix melts partially, and finally a granulated medium is formed there. To decrease the processes of heat and mass transfer in this system, the equations of dynamics of multiphase multivelocity media are derived in this study. In contrast to the Darcy-type models used in previous studies, the suggested two-velocity hydrodynamics theory describing fluid motions in a porous medium with complex reology is the thermodynamically consistent one and allows the description of nonstationary nonlinear processes. The governing equations of the model describe both the process of filtration through the deformed porous matrix and hydrodynamics of heterophase granulated medium without pressure equilibrium in phases. The work was supported by the grants 08-05-00467, 09-05-00602, 09-05-01084 from the Russian Foundation for Basic Research.

  5. 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.

  6. The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation.

    PubMed

    Kunze, P; Seher, H; Hauser, W; Panak, P J; Geckeis, H; Fanghänel, Th; Schäfer, T

    2008-12-12

    In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (<20%), fluorite precipitation at FPW contents <60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100-200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture >10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (>80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.

  7. Replacement of zircon with baddeleyite as a likely mechanism of the formation of zoned zircon crystals in ultrabasic rocks

    NASA Astrophysics Data System (ADS)

    Anfilogov, V. N.; Krasnobaev, A. A.; Ryzhkov, V. M.; Valizer, P. M.

    2017-08-01

    The problem of the U-Pb age of zircon crystals from ultrabasic rocks is discussed in this paper. It is shown that the assumption on the xenogenic nature of zircon crystals in dunite is not consistent with the petrographic and experimental data. The results of experimental study of the zircon-baddeleyite transition and thermodynamics of the reaction of zircon replacement with baddeleyite show that these transformations are the likely way of the formation of zoned zircon crystals in dunite. Each zone of these crystals may have its own age.

  8. 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.

  9. 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.

  10. 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

  11. Current oscillations generated by precipitate formation in the mixing zone between two solutions inside a nanopore.

    PubMed

    Yusko, Erik C; Billeh, Yazan N; Mayer, Michael

    2010-11-17

    Unlike biological protein pores in lipid membranes, nanopores fabricated in synthetic materials can withstand a wide range of environmental conditions including the presence of organic solvents. This capability expands the potential of synthetic nanopores to monitor chemical reactions occurring at the interface between solutions of organic and aqueous character. In this work, nanopores fabricated in borosilicate glass or silicon nitride connected a predominantly organic solvent to an aqueous solvent, thereby generating a mixing zone between these solutions inside the pore. This configuration was exploited to precipitate small organic molecules with low aqueous solubility inside the nanopores, and concomitantly, to monitor this precipitation by the decrease of the ionic conductance through the nanopores over time. Hence, this method provides a means to induce and investigate the formation of nanoprecipitates or nanoparticles. Interestingly, precipitates with a slight electric charge were cleared from the pore, causing the conductance of the pore to return to its original value. This process repeated, resulting in stable oscillations of the ionic current. Although such oscillations might be useful in fluidic logic circuits, few conditions capable of generating oscillations in ionic currents have been reported. The frequency and amplitude of oscillations could be tuned by changing the concentration of the precipitating molecule, the pH of the electrolyte, and the applied potential bias. In addition to generating oscillations, nanopores that separate two different solutions may be useful for monitoring and mediating chemical reactions in the mixing zone between two solutions.

  12. Authigenic iron oxide formation in the estuarine mixing zone of the Yangtze River

    NASA Astrophysics Data System (ADS)

    Fan, D. J.; Neuser, R. D.; Sun, X. G.; Yang, Z. S.; Guo, Z. G.; Zhai, S. K.

    2008-02-01

    Estuaries are elementary geochemical fronts where river water and seawater mix. Within this mixing zone, iron and other non-conservative elements can undergo complex reactions to form new solid phases. In order to understand authigenic iron oxide formation in the Yangtze River Estuary, two onsite water-mixing sets of experiments were conducted, one by mixing variable amounts of unfiltered Yangtze River water with filtered East China Sea water of different salinity (set 1), the other by mixing variable amounts of filtered Yangtze River water with filtered East China Sea water of different salinity (set 2). In set 2, the minerals newly formed in the course of mixing were investigated by means of a scanning electron microscope fitted with an energy-dispersive X-ray analytical system. It was found that ferrihydrite and lepidocrocite were formed in these mixing experiments, coexisting in nearly equal amounts. These iron oxides appear as aggregated particles with a large grain-size range of several microns to more than 100 μm. The electrolytic properties of seawater played an important role in the formation of these authigenic iron oxides. Kaolinite and organic aggregates were also found in the experimentally mixed pre-filtered waters. Amounts of newly formed suspended matter (set 2) were one to three orders of magnitude lower than those of total suspended matter (TSM) (set 1). This implies that newly formed minerals represent only a very small proportion of TSM in the estuarine mixing zone of the Yangtze River.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Multiple Sand Bar Formation in the Nearshore Zone

    NASA Astrophysics Data System (ADS)

    Absalonsen, L.; Dean, R.

    2011-12-01

    Sand bars are prominent features on many beaches, and can represent a major source of morphologic change in the cross-shore profile. The breaking waves are concentrated at the bar crests, resulting in reduced energy in the landward zone. Bars respond to different wave energy conditions, slowly moving shoreward with low waves and rapidly moving offshore with higher waves. However the formation and evolution of bars on multiple barred beaches is poorly understood. The presentation will describe preliminary efforts to predict the location of sand bars in the cross-shore profile, to quantify the number of sand bars under different hydrodynamic conditions and to illustrate the capability to predict profile evolution. A wave height transformation model (Dally model), a sediment transport model and conservation model are applied. The two-dimensional wave height model establishes wave height across the nearshore zone due to wave shoaling and breaking, including wave setup and bottom stress. This model utilizes two threshold values to predict the breaking position and after breaking, in the deeper water of the bar trough, the position where the waves stabilize and start to shoal again (stability criterion). Both criteria depend on the local water depth. At present, the sediment transport model consists of three components. First, the moment of momentum due to breaking waves is transferred to the bottom as a seaward shear stress concentrated somewhat landward of the bar crest. Secondly, the onshore shear stress is due to the nonlinearity of the breaking waves. Finally, the onshore transport is magnified by the proximity of turbulence to the bottom in shallow water. This model is of the "open loop" type, thus there is no guarantee of convergence to a stable profile. The capability of the model to predict bar locations on an actual profile is illustrated as follows. A profile consisting of three bars is selected from Volusia County along the northeast Florida Atlantic

  18. 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.

  19. Thermochemistry for silicic acid formation reaction: Prediction of new reaction pathway

    NASA Astrophysics Data System (ADS)

    Mondal, Bhaskar; Ghosh, Deepanwita; Das, Abhijit K.

    2009-08-01

    Reaction between SiO 2 and water has been studied extensively using ab initio methods. The mechanism for formation of metasilicic acid SiO(OH) 2 and orthosilicic acid Si(OH) 4 has been explored and a new pathway for formation of Si(OH) 4 is predicted. Heats of reaction ( ΔrH298∘) and heats of formation ( ΔfH298∘) at 298 K for the related reactions and species calculated at two different theoretical levels G3B3 and G3MP2B3 agree well with the literature values. It is found that when SiO 2 reacts simultaneously with two water molecules, the thermodynamic as well as kinetic feasibility of the process is much greater than that when SiO 2 reacts with one molecule of water.

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

    SciTech Connect

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

    2016-05-28

    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 $\\alpha$-O cleavage reaction is lower than that of the $\\beta$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

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

    DOE PAGES

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; ...

    2016-05-28

    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 themore » $$\\alpha$$-O cleavage reaction is lower than that of the $$\\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.« less

  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.

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

    SciTech Connect

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

    2016-05-28

    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 $\\alpha$-O cleavage reaction is lower than that of the $\\beta$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

  4. 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

  5. EXFOR systems manual: Nuclear reaction data exchange format

    SciTech Connect

    McLane, V.

    1996-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. 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. The exchange format, as outlined, is designed to allow 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).

  6. Modeling the cathode compartment of polymer electrolyte fuel cells: Dead and active reaction zones

    SciTech Connect

    Kulikovsky, A.A.; Divisek, J.; Kornyshev, A.A.

    1999-11-01

    A two-dimensional model of the cathode compartment of a polymer electrolyte fuel cell has been developed. The existence of gas channels in the current collector is taken into account. The model is based on continuity equations for concentrations of the gases and Poisson's equations for potentials of membrane and carbon phase, coupled by Tafel relation for reaction kinetics. Stefan-Maxwell and Knudsen diffusion of gases are taken into account. The simulations were performed for high and low values of carbon phase conductivity. The results revealed (i) for a low value of carbon phase conductivity, a dead zone in the active layer in front of the gas channel is formed, where the reaction rate is small. The catalyst may be removed from this zone without significant loss in cell performance; (ii) For a high carbon phase conductivity value, such a zone is absent, but removal of the catalyst from the same part of the active layer forces the reaction to proceed more rapidly in the remaining parts, with only marginal losses in performance. This conclusion is valid for high diffusivity of oxygen. For low diffusivity, dead zones are formed in front of the current collector, so that catalyst can be removed from these zones. The results, thus, show the possibilities for a considerable reduction of the amount of catalyst.

  7. Buffering dissociation/formation reaction of biogenic calcium carbonate.

    PubMed

    Ichikawa, Kazuhiko

    2007-01-01

    The oscillating stability of coral reef seawater pH has been maintained at around physiological pH values over the past 300 years (Pelejero et al., 2005). The stability mechanism of its pH has been interpreted in terms of the buffering dissolution/formation reaction of CaCO(3) as well as the proton consumption/generation reaction in CaCO(3)-saturated water. Here the pH-dependent solubility product [HCO(3)(-)][Ca(2+)] has been derived on the basis of the actual pH-dependent reactions for the atmospheric CO(2)/CO(2 (aq.))/HCO(3)(-)/CO(3)(2-)/Ca(2+)/CaCO(3) system. Overbasic pH peaks appeared between pH approximately 8 and approximately 9.5 during sodium hydroxide titration, as a result of simultaneous CaCO(3) formation and proton generation. The spontaneous and prompt water pH recovery from the acidic to the physiological range has been confirmed by the observation of acid/base time evolution, because of simultaneous CaCO(3) dissolution and proton consumption. The dissolution/formation of CaCO(3) in water at pH 7.5-9 does not take place without a proton consumption/generation reaction, or a buffering chemical reaction of HCO(3)(-)+Ca(2+)right arrow over left arrowCaCO(3)+H(+). SEM images of the CaCO(3) fragments showed that the acid water ate away at the CaCO(3) formed at physiological pH values. Natural coral reefs can thus recover the physiological pH levels of seawater from the acidic range through partial dissolution of their own skeletons.

  8. Preliminary Study of Coupling Electrical Energy to Detonation Reaction Zone of Primasheet-1000 Explosive

    DTIC Science & Technology

    2013-05-01

    Preliminary Study of Coupling Electrical Energy to Detonation Reaction Zone of Primasheet-1000 Explosive by Thuvan Piehler, Charles Hummer...1000 Explosive Thuvan Piehler, Charles Hummer, Richard Benjamin, Eugene Summers, and Kevin McNesby Weapons and Materials Research Directorate...5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Thuvan Piehler, Charles Hummer, Richard Benjamin, Eugene Summers, Kevin McNesby

  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. Catalysis of Dialanine Formation by Glycine in the Salt-Induced Peptide Formation Reaction.

    NASA Astrophysics Data System (ADS)

    Suwannachot, Yuttana; Rode, Bernd M.

    1998-02-01

    Mutual catalysis of amino acids in the salt-induced peptide formation (SIPF) reaction is demonstrated for the case of glycine/alanine. The presence of glycine enhances dialanine formation by a factor up to 50 and enables dialanine formation at much lower alanine concentrations. The actual amounts of glycine play an important role for this catalytic effect, the optimal glycine concentration is 1/8 of the alanine concentration. The mechanism appears to be based on the formation of the intermediate Gly-Ala-Ala tripeptide, connected to one coordination site of copper(II) ion, and subsequent hydrolysis to dialanine and glycine.

  11. 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.

  12. 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)

  13. 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.

  14. 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

  15. Thermal behavior in the cracking reaction zone of scramjet cooling channels at different channel aspect ratios

    NASA Astrophysics Data System (ADS)

    Zhang, Silong; Feng, Yu; Jiang, Yuguang; Qin, Jiang; Bao, Wen; Han, Jiecai; Haidn, Oskar J.

    2016-10-01

    To study the thermal behavior in the cracking reaction zone of regeneratively cooled scramjet cooling channels at different aspect ratios, 3-D model of fuel flow in terms of the fuel's real properties and cracking reaction is built and validated through experiments. The whole cooling channel is divided into non-cracking and cracking reaction zones. Only the cracking reaction zone is studied in this article. The simulation results indicate that the fuel conversion presents a similar distribution with temperature because the fuel conversion in scramjet cooling channels is co-decided by the temperature and velocity but the temperature plays the dominate role. For the cases given in this paper, increasing the channel aspect ratio will increase the pressure drop and it is not beneficial for reducing the wall temperature because of the much severer thermal stratification, larger conversion non-uniformity, the corresponding M-shape velocity profile which will cause local heat transfer deterioration and the decreased chemical heat absorption. And the decreased chemical heat absorption caused by stronger temperature and conversion non-uniformities is bad for the utilization of chemical heat sink, chemical recuperation process and the ignition performance.

  16. Reaction Zone Structure of Steady-State Detonation Wave for Tetranitromethane

    NASA Astrophysics Data System (ADS)

    Utkin, Alexander; Mochalova, Valentina; Garanin, Victor

    2007-06-01

    The investigation of the reaction zone structure at steady-state detonation in liquid TNM by means of laser interferometer VISAR was conducted. The initial density and detonation velocity of TNM were 1.64 g/cm^3 and 6.4 km/s respectively. Laser beam reflected from Al foil with thickness 7-400 mkm placed between the charge and water window. Velocity profiles with Von Neumann spike were determined. The transition from the reaction zone to unloading wave is smooth and it doesn't allow to define correctly the parameters of Chapman-Jouguet point. Approximate reaction time is 300 ns, and pressure in Von Neumann spike (26,4 GPa) exceeds the pressure in Chapman-Jouguet point (14,5 GPa) 1,8 times. Behind the shock jump a maximum gradient of particle velocity is observed which is equal to 10^7 1/s, it is a typical value for powerful HE. Although TNM has low parameters in Chapman-Jouguet point and a large duration of chemical reaction zone, the high initial decomposition rate provides the existence of steady-state detonation front in tetranitromethane.

  17. 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.

  18. Thermodynamics and Reaction Pathways of Furfuryl Alcohol Oligomer Formation

    SciTech Connect

    Kim, Taejin; Surendran Assary, Rajeev; Pauls, Richard E.; Marshall, Christopher L.; Curtiss, Larry A.; Stair, Peter C.

    2014-01-01

    The acid-catalyzed transformation of furfuryl alcohol (FA) monomer to oligomers has been studied in the liquid phase to investigate the reaction mechanisms and intermediate species by using a combination of quantitative reaction product measurements and density functional theory calculations. FA monomer was converted into oligomers with a broad range of carbon number: C9–C10, C14–C15, C19–C29, NC29. Based on the calculations, terminal CH2OH dimer formation is both kinetically and thermodynamically favored, consistent with the experimental results. The order for dimer production in the C9–C10 range follows terminal CH2OH N ether bridged–methylene bridged dimer N OH-carbon bridge.

  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. Reaction-zone expansions and mechanism of the O{sub 2}, Ag/yttria-stabilized zirconia electrode reaction

    SciTech Connect

    Jimenez, R.; Kloidt, T.; Kleitz, M.

    1997-02-01

    Experimental data obtained by impedance spectroscopy with silver droplet electrodes of different radii have been reanalyzed in the medium-frequency range under the assumption of rate-limiting oxygen diffusion through a thin slab of the electrode material. The model, which is based on literature data and has no adjustable parameters, gives a good fit. This demonstrates that in the medium-frequency range, oxygen diffusion through the electrode material is evenly distributed over the whole electrode interface. On the other hand, under dc conditions it is concentrated along the electrode triple-phase perimeter. Therefore, the distribution of the transfer current over the interface varies with the applied signal frequency. It follows that the electrode resistance and capacitance determined from the impedance diagram are related to an electrode reaction occurring over a reaction zone variable with the signal frequency.

  1. 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.

  2. 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.

  3. Ignition and growth modeling of detonation reaction zone experiments on single crystals of PETN and HMX

    NASA Astrophysics Data System (ADS)

    White, Bradley W.; Tarver, Craig M.

    2017-01-01

    It has long been known that detonating single crystals of solid explosives have much larger failure diameters than those of heterogeneous charges of the same explosive pressed or cast to 98 - 99% theoretical maximum density (TMD). In 1957, Holland et al. demonstrated that PETN single crystals have failure diameters of about 8 mm, whereas heterogeneous PETN charges have failure diameters of less than 0.5 mm. Recently, Fedorov et al. quantitatively determined nanosecond time resolved detonation reaction zone profiles of single crystals of PETN and HMX by measuring the interface particle velocity histories of the detonating crystals and LiF windows using a PDV system. The measured reaction zone time durations for PETN and HMX single crystal detonations were approximately 100 and 260 nanoseconds, respectively. These experiments provided the necessary data to develop Ignition and Growth (I&G) reactive flow model parameters for the single crystal detonation reaction zones. Using these parameters, the calculated unconfined failure diameter of a PETN single crystal was 7.5 +/- 0.5 mm, close to the 8 mm experimental value. The calculated failure diameter of an unconfined HMX single crystal was 15 +/- 1 mm. The unconfined failure diameter of an HMX single crystal has not yet been determined precisely, but Fedorov et al. detonated 14 mm diameter crystals confined by detonating a HMX-based plastic bonded explosive (PBX) without initially overdriving the HMX crystals.

  4. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    PubMed Central

    Lasken, Roger S; Stockwell, Timothy B

    2007-01-01

    Background Multiple Displacement Amplification (MDA) is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts) in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications. PMID:17430586

  5. Reactions of OH and Cl with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate

    NASA Astrophysics Data System (ADS)

    Zhang, Y. J.; Liang, P.; Jiang, Z. H.; Cazaunau, M.; Daële, V.; Mu, Y. J.; Mellouki, A.

    2014-05-01

    The rate coefficients for the reactions of OH with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate have been determined using both absolute and relative methods. The relative rate method has been also used to measure the room temperature rate coefficient for the reaction of Cl with the same esters. In addition, a series of runs conducted on the OH-initiated oxidation of isopropyl formate, isobutyl formate and n-propyl isobutyrate showed the formation of acetone from the three reactions. The formation of propanal was also observed for n-propyl isobutyrate.

  6. Aerosol formation yields from the reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Tomas, Alexandre; Guilloteau, Angélique; Henry, Françoise; Ledoux, Frédéric; Visez, Nicolas; Riffault, Véronique; Wenger, John C.; Bedjanian, Yuri

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. 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 catechol concentrations, assuming a particle density of 1.4 g cm -3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas-particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.

  7. 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.

  8. 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.

  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. Formation of superheavy elements in cold fusion reactions

    SciTech Connect

    Smolanczuk, 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 {sup 209}Bi({sup 86}Kr, 1n){sup 294}119, {sup 208}Pb({sup 88}Sr, 1n){sup 295}120, and {sup 209}Bi({sup 88}Sr, 1n){sup 296}121, 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 {sup 136}Xe({sup 124}Sn, 1n){sup 259}Rf, {sup 136}Xe({sup 136}Xe, 1n){sup 271}Hs,{sup 138}Ba({sup 136}Xe, 1n){sup 273}110, and {sup 140}Ce({sup 136}Xe, 1n){sup 275}112. Although shell effects in the magic nuclei {sup 124}Sn, {sup 136}Xe, {sup 138}Ba, and {sup 140}Ce are not as strong as in {sup 208}Pb and {sup 209}Bi, they act on both the target and the projectile and lead to the prediction of measurable cross sections.

  11. Kartogenin with PRP promotes the formation of fibrocartilage zone in the tendon-bone interface.

    PubMed

    Zhou, Yiqin; Zhang, Jianying; Yang, Jinsong; Narava, Manoj; Zhao, Guangyi; Yuan, Ting; Wu, Haishan; Zheng, Nigel; Hogan, MaCalus V; Wang, James H-C

    2017-01-27

    Treatment of tendon-bone junction injuries is a challenge because tendon-bone interface often heals poorly and the fibrocartilage zone, which reduces stress concentration, at the interface is not formed. In this study, we used a compound called kartogenin (KGN) with platelet-rich plasma (PRP) to induce the formation of fibrocartilage zone in a rat tendon graft-bone tunnel model. The experimental rats received KGN-PRP or PRP injections in the tendon graft-bone tunnel interface. The control group received saline. After 4, 8 and 12 weeks, Safranin O staining of the tendon graft-bone tunnels revealed abundant proteoglycans in the KGN-PRP group indicating the formation of cartilage-like transition zone. Immunohistochemical and immuno-fluorescence staining revealed collagen types I (Col-I) and II (Col-II) in the newly formed fibrocartilage zone. Both fibrocartilage zone formation and maturation were healing time dependent. In contrast, the PRP and saline control groups had no cartilage-like tissues and minimal Col-I and Col-II staining. Some gaps were also present in the saline control group. Finally, pull-out strength in the KGN-PRP-treated group at 8 weeks was 1.4-fold higher than the PRP-treated group and 1.6-fold higher than the saline control group. These findings indicate that KGN, with PRP as a carrier, promotes the formation of fibrocartilage zone between the tendon graft and bone interface. Thus, KGN-PRP may be used as a convenient cell-free therapy in clinics to promote fibrocartilage zone formation in rotator calf repair and anterior cruciate ligament reconstruction, thereby enhancing the mechanical strength of the tendon-bone interface and hence the clinical outcome of these procedures. Copyright © 2017 John Wiley & Sons, Ltd.

  12. The Formation of Cores of Giant Planets at Convergence Zones of Planetary Migration

    NASA Astrophysics Data System (ADS)

    Sirono, Sin-iti; Katayama, Masahumi

    2016-10-01

    The formation of solid cores in giant planets of mass ∼ 10 {M}\\oplus is numerically simulated following the scenario of Sándor et al. In this scenario, there are two convergence zones, corresponding to the outer and inner edges of the dead zone, where the torque exerted on planetary embryos by the gas nebula is zero. At the outer edge of the dead zone, anticyclonic vortices accumulate infalling dust aggregates, and planetary embryos are continuously formed in this scenario. We performed N-body simulations and show that massive objects of ≃ 10 {M}\\oplus are formed in ∼2.5 Myr, starting from the embryos. The largest object is formed at the inner convergence zone, although planetary embryos are placed at the outer convergence zone. This is due to the scattering of embryos from the outer to the inner convergence zone, and the shorter damping timescale of eccentricity at the inner convergence zone compared to the outer one. We varied the migration timescale due to the torque from gas by changing the gas surface density around the convergence zones. We found that there is a critical migration timescale below which 10 {M}\\oplus -sized objects are formed. Furthermore, we conducted simulations in which the gas surface density evolves according to viscous accretion. The largest object is also formed at the inner convergence zone irrespective of the strength of turbulence. Throughout the simulations, the location of the largest mass is the inner convergence zone. We confirmed that the formation timescale of a core of a Jovian planet can be explained in this scenario.

  13. Experimental Astrochemistry: Molecular Formation via Grain-Surface Reactions

    NASA Astrophysics Data System (ADS)

    Congiu, E.

    2007-03-01

    Central to this thesis is the chemistry occurring on dust grain surfaces leading to the formation of molecules in the ISM, and, in particular, the laboratory simulation of formation mechanisms and formation rates. Surface chemistry plays a crucial role in the ISM because it produces key species that are not formed in gas-phase reactions at an efficient rate. Among them, molecular hydrogen (H_2) is by far the most important. In this work (Chapter 3), I shall address the experimental investigation of H_2 formation on diverse samples of amorphous silicates. The experimental work was conducted in the Physics Department laboratories at Syracuse University, New York, as part of the most successful programme of experiments so far to study the processes involved in the formation of molecular hydrogen on a variety of dust analogue materials, also including poly-crystalline olivine, amorphous carbon, and ices. The experiments were carried out through mass spectrometry and TPD techniques and under conditions that come as close as technically feasible to the ones in the most relevant ISM environments, namely, under ultra high vacuum pressures (low 10e-10 torr) and at surface temperatures between 6 and 30 K. Experimental studies of H_2 formation on amorphous olivines are of major concern in grain-surface chemistry because amorphous silicates are believed, together with carbonaceous materials, to be the most realistic analogues of bare cosmic dust surfaces in diffuse clouds. In my doctorate work I carried out numerous experiments on a set of several samples of amorphous olivines of the type (Mg_x,Fe_1-x)_2SiO_4, namely, samples made up of diverse amounts of Mg and Fe. Besides, in Chapter 4, I shall address the project and the construction of a FT-RAIRS facility that is to integrate the existent research apparatus in the laboratory at Syracuse University. I shall first discuss the FT-IR spectroscopy, then I shall focus on a particular technique used in surface science called

  14. 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.

  15. 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.

  16. 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.

  17. Subglacial till formation: Microscale processes within the subglacial shear zone

    NASA Astrophysics Data System (ADS)

    Hart, Jane K.

    2017-08-01

    This was a study of subglacial deformation till genesis from a modern temperate glacier, at Skálafellsjökull, Iceland. Detailed microscale properties of till samples (from Scanning Electron Microscope [SEM] and thin section analysis) were examined from a glacial site with in situ subglacial process monitoring and an exposed subglacial surface in the foreland. Two lithofacies were examined, a grey sandy till derived from the ash and basalt, and a silty reddish brown till derived from oxidized paleosols and/or tephra layers. These also represented a clay-content continuum from low (0.3%) to high (22.3%). The evolution from debris to subglacial till was investigated. This included a reduction in grain-size (21% for grey lithology, 13% reddish brown lithology), and reduction in rounding (RA) (32% for the grey lithology, 26% for the reddish brown lithology), and the quantification and analysis of the different grain erosion/comminution processes in the resultant till. It was shown that the microstructures within a till were dependent on shear strain and glaciological conditions (deformation history). The low clay content tills were dominated by linear structures (lineations and boudins, and anisotropic microfabric) whilst the higher clay content tills were dominated by rotational structures (turbates and plaster, and isotropic microfabric). These results are important in our understanding of the formation of both modern and Quaternary tills and informs our reconstruction of past glacial dynamics.

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

    PubMed

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

    2004-02-05

    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.

  19. 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.

  20. 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

  1. Ammonite zonation in condensed zone, middle Ozan formation (Taylor group, upper Cretaceous) in Northeast Texas

    SciTech Connect

    Echols, J.

    1984-04-01

    Recognition of condensed zones is important because they may be marker horizons that are useful in exploration. Such a zone is demonstrated by the occurrence of ammonites belonging to 12 species and 9 genera from the middle Ozan Formation (lower Taylor Marl) in northeast Texas. The 1-foot (0.3-m) thick bed of bioturbated glauconitic biomicrite contains many specimens of disarticulated vertebrates, molluscs, remanie' fossils (blackened phosphatic internal molds), and hiatus concretions. Four of 6 midcontinent ammonite range zones proposed by Cobban and others appear to be represented in the fauna, in ascending order, by Baculites aquilaensis Reeside, Delawarella delawarensis (Morton) (= zones of two unnamed species of Baculites), Baculites obtusus Meek, and Trachyscaphites spiniger porchi Adkins (=zones of Baculites mclearni and B. asperiformis). Young may be correct in assuming that the occurrence of Delawarella delawarensis and Baculites aquilaensis in the Ozan Formation may mean that rocks of the upper Austin Group and parts of the lower Taylor Group are the same age. If correlation with the midcontinent zonation is correct, then the sediments that formed the condensed zone slowly accumulated from 81 to 79 m.y. (mid early Campanian to early late Campanian). Several species of the fauna are preserved as both normal and remanie' fossils, indicating that members of these species lived in the area for an extended period of time, perhaps as a relict fauna. The fauna includes a mixture of cosmopolitan and endemic species (indicating open shelf environment) with several types of heteromorphs (indicating moderate water depths).

  2. 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.

  3. Microearthquakes Beneath the Endeavour Hydrothermal Vent Fields: Insights Into Reaction Zone Processes

    NASA Astrophysics Data System (ADS)

    Wilcock, W. S.; Hooft, E. E.; McGill, P. R.; Toomey, D. R.; Barclay, A. H.; Stakes, D. S.; Ramirez, T. M.

    2007-12-01

    From 2003-2006, a novel seismic network comprising seven short-period corehole seismometers and a broadband Guralp CMG-1T OBS was deployed using remotely operated vehicles in a subseafloor configuration on the Endeavour segment of the Juan de Fuca mid-ocean ridge. The seismic monitoring array was one part of a multi-disciplinary prototype NEPTUNE experiment designed to investigate the linkages between seismic deformation, hydrothermal fluxes, and microbial productivity along oceanic plate boundaries. The seismic network recorded high-quality data that illustrate the advantages of using an ROV to deploy seismometers in well- coupled configurations that are also away from the effects of ocean currents. A preliminary analysis of the first year of Keck seismic data was undertaken during a research apprenticeship class taught in the fall of 2004 at the University of Washington's Friday Harbor Laboratories. Eight post- baccalaureate students obtained a preliminary catalog of nearly 13,000 earthquakes on the Endeavour segment. Two of the apprentices conducted a second-pass analysis to refine the locations of ~3000 earthquakes that are within or near the network. Further analysis of these proximal earthquakes has focused on the application of cross-correlation and relative relocation techniques, the determination of focal mechanisms using P-wave first motions and P- to S-wave amplitudes ratios, and improved estimates of earthquake magnitudes. The results show that the entire Endeavour segment was seismically active during 2003-2004. Within the network, the earthquakes are located in tight clusters centered at ~2 km depth in the inferred location of the hydrothermal reaction zone immediately above a crustal magma chamber imaged by seismic reflection studies. The number of earthquakes below each hydrothermal vent field correlates with the heat flux measured by other researchers and the vertical thickness of this reaction zone, inferred from the distribution of seismicity, is

  4. Authigenic mineral formation in fluid permeability zones in the West Siberia Permafrost

    NASA Astrophysics Data System (ADS)

    Kurchatova, A. N.; Melnikov, V. P.; Rogov, V. V.; Slagoda, E. A.

    2016-06-01

    Basic chemical and mineralogical anomalies in permafrost caused by hydrocarbon migration are considered. Direct evidence for bacterial oxidation of light hydrocarbons, primarily methane, were first obtained in fluid permeability zones in the permafrost as a stepwise formation of authigenic minerals such as iron sulfides and oxides, carbonates, silicates, and gypsum.

  5. Formate as an energy source for microbial metabolism in chemosynthetic zones of hydrothermal ecosystems.

    PubMed

    Windman, Todd; Zolotova, Natalya; Schwandner, Florian; Shock, Everett L

    2007-12-01

    Formate, a simple organic acid known to support chemotrophic hyperthermophiles, is found in hot springs of varying temperature and pH. However, it is not yet known how metabolic strategies that use formate could contribute to primary productivity in hydrothermal ecosystems. In an effort to provide a quantitative framework for assessing the role of formate metabolism, concentration data for dissolved formate and many other solutes in samples from Yellowstone hot springs were used, together with data for coexisting gas compositions, to evaluate the overall Gibbs energy for many reactions involving formate oxidation or reduction. The result is the first rigorous thermodynamic assessment of reactions involving formate oxidation to bicarbonate and reduction to methane coupled with various forms of iron, nitrogen, sulfur, hydrogen, and oxygen for hydrothermal ecosystems. We conclude that there are a limited number of reactions that can yield energy through formate reduction, in contrast to numerous formate oxidation reactions that can yield abundant energy for chemosynthetic microorganisms. Because the energy yields are so high, these results challenge the notion that hydrogen is the primary energy source of chemosynthetic microbes in hydrothermal ecosystems.

  6. 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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

    Powers, Joseph M.; Gonthier, Keith A.

    1992-09-01

    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.

  9. 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.

  10. Modelling of Turbulent Scalar Fluxes in the Broken Reaction Zones Regime

    NASA Astrophysics Data System (ADS)

    Im, Hong G.; Chakraborty, Nilanjan; Klein, Markus; Kasten, Christian; Arias, Paul

    2016-11-01

    The LES filtered species transport equation in turbulent reacting flow simulations contains the unclosed turbulent scalar flux that needs to be modelled. It is well known that the statistical behavior of this term and its alignment characteristics with resolved scalar gradient depend on the relative importance of heat release and turbulent velocity fluctuations. Counter-gradient transport has been reported in several earlier studies where the flames under investigation were located either in the corrugated flamelets or thin reaction zones regime of premixed turbulent combustion. Therefore it is useful to understand the statistical behavior of turbulent scalar fluxes if the flame represents the broken reaction zones regime (BRZR). The present analysis aims to provide improved understanding on this subject through an a-priori analysis of a detailed chemistry database consisting of three freely-propagating statistically planar turbulent H2-air premixed flames representing three different regimes of combustion. Results indicate that heat release effects weaken with increasing Karlovitz number, but that counter-gradient transport can still occur for large LES filter size in the BRZR. Furthermore the behaviour of the flux and in particular its sign are different for reactant and product species. KAUST, EPSRC, KAUST Supercomputing Lab, N8, Archer.

  11. 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.

  12. Ionic liquid effects on Mizoroki-Heck reactions: more than just carbene complex formation.

    PubMed

    Gyton, Matthew R; Cole, Marcus L; Harper, Jason B

    2011-08-28

    Reaction profiles for a Mizoroki-Heck reaction in either an ionic liquid or a molecular solvent with different palladium sources demonstrate that the rate enhancements observed in ionic liquids cannot be solely attributed to Pd-carbene complex formation.

  13. 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.

  14. 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.

  15. Sources of inner radiation zone energetic helium ions: cross-field transport versus in-situ nuclear reactions.

    PubMed

    Spjeldvik, W N; Pugacheva, G I; Gusev, A A; Martin, I M; Sobolevsky, N M

    1998-01-01

    Radial transport theory for inner radiation zone MeV He ions has been extended by combining radial diffusive transport, losses due to Coulomb friction and charge exchange reaction with local generation of 3He and 4He ions due to nuclear reactions taking place on the inner edge of the inner radiation zone. From interactions between high energy trapped protons and upper atmospheric constituents we have included a nuclear reaction yield helium flux source that was numerically derived from a nuclear reaction model originally developed at the Institute of Nuclear Researches of Moscow, Russia and implemented in the computer system at the University of Campinas, Brazil. Magnetospheric transport computations have been made covering the L-shell range L=1.0 to 1.6 and the resulting MeV He ion flux distributions show a strong influence of the local nuclear source mechanism on the inner zone energetic He ion content.

  16. Subducted banded iron formations as a source of ultralow-velocity zones at the core-mantle boundary.

    PubMed

    Dobson, David P; Brodholt, John P

    2005-03-17

    Ultralow-velocity zones (ULVZs) are regions of the Earth's core-mantle boundary about 1-10 kilometres thick exhibiting seismic velocities that are lower than radial-Earth reference models by about 10-20 per cent for compressional waves and 10-30 per cent for shear waves. It is also thought that such regions have an increased density of about 0-20 per cent (ref. 1). A number of origins for ULVZs have been proposed, such as ponding of dense silicate melt, core-mantle reaction zones or underside sedimentation from the core. Here we suggest that ULVZs might instead be relics of banded iron formations subducted to the core-mantle boundary between 2.8 and 1.8 billion years ago. Consisting mainly of interbedded iron oxides and silica, such banded iron formations were deposited in the world's oceans during the late Archaean and early Proterozoic eras. We argue that these layers, as part of the ocean floor, would be recycled into the Earth's interior by subduction, sink to the bottom of the mantle and may explain all of the observed features of ULVZs.

  17. 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.

  18. Currents and voltages in the MFTF coils during the formation of a normal zone

    SciTech Connect

    Owen, E.W.

    1980-08-01

    Expressions are obtained for the currents and voltages in a pair of inductively coupled superconducting coils under two conditions: formation of a normal zone and during a change in the level of the current in one coil. A dump resistor of low resistance and a detector bridge is connected across each coil. Calculated results are given for the MFTF coils. The circuit equations during formation of a normal zone are nonlinear and time-varying, consequently, only a series solution is possible. The conditions during a change in current are more easily found. After the transient has died away, the voltages in the coil associated with the changing source are all self-inductive, while the voltages in the other coil are all mutually inductive.

  19. 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

  20. Self-consistent orogenic wedge formation and shear zone propagation due to thermal softening

    NASA Astrophysics Data System (ADS)

    Jaquet, Yoann; Duretz, Thibault; Schmalholz, Stefan M.

    2016-04-01

    We present two dimensional numerical simulations of orogenic wedge formation for a viscoelastoplastic lithosphere under compression. The thermo-mechanical model is based on the principle of energy conservation and includes temperature-dependent rheologies. With this approach, shear zones caused by thermal softening develop spontaneously in the absence of strain softening. The initial locus of shear localization is controlled by either lateral temperature variations (100°C) at the model base or by lateral variations in crustal thickness. The first episode of strain localization occurs after 15% bulk shortening. With ongoing strain, a series of shear zones arise and propagate towards the foreland leading to the self-consistent formation of an orogenic wedge. We investigate the impact of bulk shortening rates, erosion and rheology on the dynamics of wedge formation, the associated topography and uplift rates. The maximum topography reaches up to 10 km and the surface morphology evolves according to shear zone activation and deactivation. Uplift rates are transient and peak values are maintained only on very short time scales. A running average of the uplift rate versus time curves with a time-window of 4 My provides average uplift rates in the order of a few millimeters per year. Erosion is an important parameter for the formation and the evolution of the wedge (e.g. can control the spacing of shear zones by modifying crustal thickness). Rheological parameters, such as the friction angle or the upper crustal viscosity, control the occurrence of strain localization. Bulk shortening rates between 10-15 and 10-16 s-1 do not have a major impact on the resulting wedge structure.

  1. 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.

  2. Characterization and modeling of premixed turbulent n-heptane ames in the thin reaction zone regime

    NASA Astrophysics Data System (ADS)

    Savard, Bruno

    n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar'' non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally

  3. 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.

  4. The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

    NASA Astrophysics Data System (ADS)

    Guan, Jinan; Liang, Deqing; Wu, Nengyou; Fan, Shuanshi

    2009-10-01

    It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m -2 a -1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10 9 m 3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

  5. Body-Fitted Detonation Shock Dynamics and the Pseudo-Reaction-Zone Energy Release Model

    NASA Astrophysics Data System (ADS)

    Meyer, Chad; Quirk, James; Short, Mark; Chqiuete, Carlos

    2016-11-01

    Programmed-burn methods are a class of models used to propagate a detonation wave, without the high resolution cost associated with a direct numerical simulation. They separate the detonation evolution calculation into two components: timing and energy release. The timing component is usually calculated with a Detonation Shock Dynamics model, a surface evolution representation that relates the normal velocity of the surface (Dn) to its local curvature. The energy release component must appropriately capture the degree of energy change associated with chemical reaction while simultaneously remaining synchronized with the timing component. The Pseudo-Reaction-Zone (PRZ) model is a reactive burn like energy release model, converting reactants into products, but with a conversion rate that is a function of the DSD surface Dn field. As such, it requires the DSD calculation produce smooth Dn fields, a challenge in complex geometries. We describe a new body-fitted approach to the Detonation Shock Dynamics calculation which produces the required smooth Dn fields, and a method for calibrating the PRZ model such that the rate of energy release remains as synced as possible with the timing component. We show results for slab, rate-stick and arc geometries.

  6. Asymmetric hollow nanorod formation through a partial galvanic replacement reaction.

    PubMed

    Seo, Daeha; Song, Hyunjoon

    2009-12-30

    An asymmetric single hollow structure was generated from Ag-Au-Ag heterometal nanorods by a partial galvanic replacement reaction for the first time. The C(2)-symmetry breaking took place because of the random generation of a single pit on only one end of the silver domain at an early stage of the reaction. Careful control of the reaction kinetics could also yield a double-hollow structure on both ends of the silver domain. The resulting single- and double-hollow nanorods exhibited characteristic extinctions in the near-IR range.

  7. 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.

  8. Vortex formation and recirculation zones in left anterior descending artery stenoses: computational fluid dynamics analysis

    NASA Astrophysics Data System (ADS)

    Katritsis, D. G.; Theodorakakos, A.; Pantos, I.; Andriotis, A.; Efstathopoulos, E. P.; Siontis, G.; Karcanias, N.; Redwood, S.; Gavaises, M.

    2010-03-01

    Flow patterns may affect the potential of thrombus formation following plaque rupture. Computational fluid dynamics (CFD) were employed to assess hemodynamic conditions, and particularly flow recirculation and vortex formation in reconstructed arterial models associated with ST-elevation myocardial infraction (STEMI) or stable coronary stenosis (SCS) in the left anterior descending coronary artery (LAD). Results indicate that in the arterial models associated with STEMI, a 50% diameter stenosis immediately before or after a bifurcation creates a recirculation zone and vortex formation at the orifice of the bifurcation branch, for most of the cardiac cycle, thus allowing the creation of stagnating flow. These flow patterns are not seen in the SCS model with an identical stenosis. Post-stenotic recirculation in the presence of a 90% stenosis was evident at both the STEMI and SCS models. The presence of 90% diameter stenosis resulted in flow reduction in the LAD of 51.5% and 35.9% in the STEMI models and 37.6% in the SCS model, for a 10 mmHg pressure drop. CFD simulations in a reconstructed model of stenotic LAD segments indicate that specific anatomic characteristics create zones of vortices and flow recirculation that promote thrombus formation and potentially myocardial infarction.

  9. 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.

  10. Transient cnoidal waves explain the formation and geometry of fault damage zones

    NASA Astrophysics Data System (ADS)

    Veveakis, Manolis; Schrank, Christoph

    2017-04-01

    The spatial footprint of a brittle fault is usually dominated by a wide area of deformation bands and fractures surrounding a narrow, highly deformed fault core. This diffuse damage zone relates to the deformation history of a fault, including its seismicity, and has a significant impact on flow and mechanical properties of faulted rock. Here, we propose a new mechanical model for damage-zone formation. It builds on a novel mathematical theory postulating fundamental material instabilities in solids with internal mass transfer associated with volumetric deformation due to elastoviscoplastic p-waves termed cnoidal waves. We show that transient cnoidal waves triggered by fault slip events can explain the characteristic distribution and extent of deformation bands and fractures within natural fault damage zones. Our model suggests that an overpressure wave propagating away from the slipping fault and the material properties of the host rock control damage-zone geometry. Hence, cnoidal-wave theory may open a new chapter for predicting seismicity, material and geometrical properties as well as the location of brittle faults.

  11. 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

  12. 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

  13. 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

  14. Reaction path and crystallograpy of cobalt silicide formation on silicon(001) by reaction deposition epitaxy

    NASA Astrophysics Data System (ADS)

    Lim, Chong Wee

    CaF2-structure CoSi2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi2 layers obtained by conventional solid phase growth (SPG). In the case of RDE, CoSi 2 formation occurred during Co deposition at elevated temperature while for SPG, Co was deposited at 25°C and silicidation took place during subsequent annealing. My results demonstrate that RDE CoSi2 layers are epitaxial with a cube-on-cube relationship, 001CoSi2 ‖001Si and 100CoSi2 ‖100 Si . In contrast, SPG films are polycrystalline with a mixed 111/002/022/112 orientation. I attribute the striking difference to rapid Co diffusion during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. Initial formation of CoSi2(001) follows the Volmer-Weber mode with two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal <110> directions, bounded by four {111} CoSi2/Si interfaces, and grow with a cube-on-cube orientation with respect to Si(001). Platelet-shaped islands are bounded across their long <110> directions by {111} twin planes and their narrow <110> directions by 511CoSi2 ‖111Si interfaces. The top and bottom surfaces are {22¯1}, with 22¯1 CoSi2‖001 Si , and {1¯1¯1}, with 1¯1¯ 1CoSi2‖ 11¯1Si , respectively. The early stages of film growth (tCo ≤ 13 A) are dominated by the twinned platelets due to a combination of higher nucleation rates and rapid elongation along preferred <110> directions. However, at tCo ≥ 13 A, island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. Further island growth becomes dominated by the untwinned islands. I show that high-flux low-energy Ar+ ion irradiation during RDE growth dramatically increases the area fraction of untwinned regions from 0.17 in films grown under standard magnetically balanced

  15. 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

  16. Shock Separation and Dead-Zone Formation from Detonations in an Internal Air-Well Geometry

    NASA Astrophysics Data System (ADS)

    Molitoris, John; Andreski, Henry; Garza, Raul; Batteux, Jan; Vitello, Peter; Souers, Clark

    2007-06-01

    Here we report on measurements of dead-zone formation due to shock separation from detonations attempting to corner-turn in an internal air-well geometry. This geometry is also known as a ``hockey-puck'' configuration. These measurements were performed on detonations in LX-17 and PBX9502 using time sequence radiography to image the event with surface contact timing pins as an additional diagnostic. In addition to an open corner in the high-explosive component we also examined the effects of steel defining the corner. In these experiments we find a long lived dead-zone consisting of shocked explosive that persists to very late times. Data and numerical modeling will be presented in addition to a comparison with previous work using an external air well. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  17. The influence of water on the formation of mantle shear zones

    NASA Astrophysics Data System (ADS)

    Warren, J. M.; Skemer, P. A.; Hirth, G.; Kelemen, P. B.

    2012-12-01

    The formation of localized shear zones is a prerequisite for plate tectonics, yet the mechanisms that drive shear localization are poorly constrained. In the oceanic lithosphere, ductiley-deformed peridotites have been found at detachment and transform faults, indicating the importance of mantle shear localization for plate spreading. Proposed mechanisms for initiating shear localization include water or melt addition, grain size reduction, and effects due to lattice preferred orientations (LPO). However, the sequence of physical processes that leads to ductile shear localization in the mantle lack direct geological observation for the generation of fine-grained (~1-100 μm) mylonites from coarse-grained (0.5-5 mm) protoliths. The Josephine Peridotite in Oregon provides a field setting to test hypotheses for initiation of shear localization. The massif is an obducted section of oceanic lithospheric mantle, which contains a sequence of small shear zones that vary from 1 m to 60 m wide. Measurement of the passive rotation of pyroxenite layers across the shear zones provides an estimate strain. Mylonites are observed at the center of the narrowest shear zones, which also record the highest strains (>2000 %). Field observations of the presence and abundance of syn-kinematic melt veins, consisting of gabbro or dunite, provide constraints on the role of melt in shear localization. Variations in water content appear to drive strain localization in the Josephine. Water, present as hydrogen defects in nominally anhydrous minerals (e.g., olivine, orthopyroxene) can significantly influence mantle rheology. One of the highest strain shear zones has an olivine LPO that corresponds to Type-E (001)[100] slip, whereas the LPO of the widest shear zone corresponds to Type-A (010)[100] slip. Experimental constraints on olivine LPO indicate that Type-E slip corresponds to olivine with a higher water content than Type-A slip. To confirm the role of water in shear localization, we

  18. 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

  19. 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.

  20. Viewer Reactions to Content and Presentational Format of Television News.

    ERIC Educational Resources Information Center

    Behnke, Ralph R.; Miller, Phyllis

    1992-01-01

    Investigates patterns of college-student reactions to local television newscasts. Finds that significant audience adaptation does not occur during a 30-minute newscast and that there was no relationship between segment placement and level of viewer interest. Suggests that the audience rebound phenomenon overcomes the audience adaptation phenomenon…

  1. 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

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

    SciTech Connect

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

    2016-09-02

    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. - Highlights: • Tspan7 expression is up-regulated during osteoclastogenesis. • Tspan7 regulates podosome belt organization in osteoclasts. • Tspan7 is crucial for sealing zone formation and bone-resorption by osteoclasts. • Src and Pyk2 phosphorylation and microtubule acetylation mediate Tspan7 function.

  3. 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

  4. 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

  5. Nanograin formation and reaction-induced fracturing due to decarbonation: Implications for the microstructures of fault mirrors

    NASA Astrophysics Data System (ADS)

    Pluymakers, A.; Røyne, A.

    2017-10-01

    Principal slip zones often contain highly reflective surfaces referred to as fault mirrors, shown to consist of a nanogranular coating. There is currently no consensus on how the nanograins form, or why they survive weathering on a geological time-scale. To simplify the complex system of a natural fault zone, where slip and heat generation are inherently coupled, we investigated the effect of elevated temperatures on carbonate rock surfaces, as well as their resistance to water exposure. This allows us to isolate the role of the decarbonation process in the formation of nanograins. We used cleaved crystals of Iceland spar calcite, manually polished dolomite protolith, as well as natural dolomite fault mirror surfaces. The samples were heated to 200-800 °C in a ∼5 h heating cycle, followed by slow cooling (∼12 h) to room temperature. Subsequently, we imaged the samples using scanning electron microscopy and atomic force microscopy. Nanograin formation on all sample surfaces was pervasive at and above 600 °C. The Foiana fault mirror samples were initially coated with aligned naturally-formed nanograins, but display a non-directional nanogranular coating after heating. The nanograins that were formed by heating rapidly recrystallized to bladed hydroxides upon exposure to deionized water, whereas the nanograins on unheated fault mirror samples remained unchanged in water. This shows that the nanograins formed by heating alone are different from those formed in fault zones, and calls for a better characterization of nanograins and their formation mechanisms. Furthermore, we find a characteristic star-shaped crack pattern associated with reacted regions of the carbonate surfaces. The existence of this pattern implies that the mechanical stresses set up by the decarbonation reaction can be sufficiently large to drive fracturing in these systems. We propose that this mechanism may contribute to grain size reduction in fault zones.

  6. 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

  7. 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.

  8. 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.

  9. Identification of indicators of groundwater quality formation process using a zoning model

    NASA Astrophysics Data System (ADS)

    Jing, Xiu-yan; Yang, Hongbin; Cao, Yuqing; Wang, Wenke

    2014-06-01

    Drinking water safety is a world-wide focus. In Yinchuan Plain of western China, groundwater is mostly saline water, and it has generated many problems for the life of local residents. Yinchuan Plain exhibits differences from the mountain area to the plain in terrain and elevation, and landforms and scales. Such differences resulted in hydro-geological water storage structures with different water yield properties and permeabilities of the aquifers. These water storage structures are the places where the groundwater moves and is retained, as well as where the air-water-rock interaction and the migration and differentiation between substances in the water take place. With the arid climate and intense irrigation in Yinchuan Plain, the hydro-chemical features of the groundwater exhibit distinct zonation. To explore the formative mechanism of the groundwater quality in Yinchuan Plain, a zoning model for the formation of groundwater quality is established in three layers, the first layer shows the geological and hydrogeological conditions that express the landform and landscape, geological age, lithology, and hydrodynamic features of the studied area. The second layer indicates the zonation of the formation of groundwater quality. According to the major hydro-geochemical actions, the plain is divided from west to east into lixiviation, evaporation, and evaporation-mixing zones. The third layer contains the hydrodynamic features that express the hydro-chemical type, salinity, and the contents of the major ions as well as trace elements fluorine and arsenic. The features of each zone are quantitatively expressed with thermodynamic, hydrodynamic, and hydro-chemical indicators.

  10. Modeling of perched leachate zone formation in municipal solid waste landfills.

    PubMed

    Di Bella, Gaetano; Di Trapani, Daniele; Mannina, Giorgio; Viviani, Gaspare

    2012-03-01

    The paper presents a 1D mathematical model for the simulation of the percolation fluxes throughout a landfill for municipal solid waste (MSW). Specifically, the model was based on mass balance equations, that enable simulation of the formation of perched leachate zones in a landfill for MSW. The model considers the landfill divided in several layers evaluating the inflow to and outflow from each layer as well as the continuous moisture distribution. The infiltration flow was evaluated by means of the Darcy's law for an unsaturated porous medium, while the moisture distribution evaluation has been carried out on the basis of the theory of the vertically distributed unsaturated flow. The solution of the model has been obtained by means of the finite difference method. The model has been applied to a semi-idealized landfill located in Palermo landfill (Bellolampo). Specifically, field measurements were conducted to determine the relationship between waste density and applied vertical strain. This relationship was then used to relate vertical strain to waste porosity. The inflow rate to the system was simulated via a synthetic hyetograph whose characteristics have been identified in a previous hydrologic study. Three simulations, each with a different initial moisture content, were conducted. The model results showed a different response of the landfill in terms both of flow rates throughout the landfill and moisture profile. Indeed, the initial moisture content drastically influenced not only the formation of perched leachate zones but also their extension. The model can be a useful tool in predicting potential for the formation of perched leachate zones. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Mojave-Yavapai boundary zone, southwestern United States: A rifting model for the formation of an isotopically mixed crustal boundary zone

    NASA Astrophysics Data System (ADS)

    Duebendorfer, Ernest M.; Chamberlain, Kevin R.; Fry, Bill

    2006-08-01

    The boundary between the Paleoproterozoic Mojave and Yavapai crustal provinces in the southwestern United States is a 75-km-wide zone characterized by complex, isotopically mixed (Pb) crust, similar to other transitional crustal and lithospheric boundaries worldwide. Mojave crust is more isotopically evolved than the juvenile crust of the Yavapai province, indicating an older crustal component. Several areas of isotopically juvenile rocks within and near the boundary zone correspond to exposures of coeval >1.73 Ga supracrustal rocks that contain pillow basalts and bimodal metavolcanic sequences. We suggest that regions of juvenile crust within the Mojave province and its boundary zone represent rift basins, produced by extension or transtension near the eastern margin of the province, into which primitive basaltic lavas and bimodal volcanic sequences were erupted. The largest region of juvenile material within the boundary zone is bound to the west by a series of coincident, N-trending isotopic, geochemical, metamorphic, and geophysical discontinuities that may represent a fundamental, buried crustal structure, perhaps a rift margin. We propose that the distinct isotopic signature of the boundary zone persisted through subsequent deformational events, including the one that juxtaposed the two provinces. If our model for the formation of the boundary zone is correct, its isotopically mixed character is at least partly an artifact of the precollision history of the eastern Mojave province, and may not solely reflect the processes that juxtaposed the two provinces. Formation of new crust by rifting may represent an underappreciated form of crustal growth during the Paleoproterozoic that is distinct from arc accretion. Models for the formation of complex crustal boundary zones must consider the early, prejuxtaposition history of terranes in interpreting their geochemical and geophysical characteristics.

  12. Super acid catalysis in supercritical fluid reaction media for the formation of linear alkyl benzenes.

    PubMed

    Harmer, Mark A; Hutchenson, Keith W

    2002-01-07

    High catalytic activity is demonstrated for the formation of linear alkylbenzenes using a perfluorosulfonic acid catalyst in supercritical fluid reaction media: enhanced alkylation activity is observed in fluoroform (CHF3) compared to carbon dioxide.

  13. An example of mixing-zone dolomite, Middle Eocene Avon Park Formation, Floridan aquifer system

    SciTech Connect

    Cander, H.S. )

    1994-07-01

    A late-formed dolomite cement in a core of the Middle Eocene Avon Park Formation, peninsular Florida, provides an example of dolomite cement from a mixing zone and illustrates how dolomite textural alteration and stabilization can occur at earth-surface conditions. The Avon Park Formation is a pervasively dolomitized peritidal platform carbonate 400 m thick in the Florida aquifer system. Typical Avon Park dolomite is inclusion-rich, fine-grained (< 40 mm), noncathodoluminescent, highly porous (average, 20%), and formed during the Eocene by normal to hypersaline seawater ([delta][sup 18]O = + 3.7[per thousand] PDB; [delta][sup 13]C = + 2.0[per thousand]; [sup 87]Sr/[sup 86]Sr = 0.70778; Sr = 167 ppm). In a 20 m interval in a core from southwest Florida, inclusion-free, cathodoluminescent dolomite overgrows the early-formed noncathodoluminescent marine dolomite. The cathodoluminescent dolomite cement profoundly alters the texture of Avon Park dolomite from typical Cenozoic-like porous, poorly crystalline dolomite to hard, dense, low-porosity, highly crystalline Paleozoic-like dolomite. The dolomite cement is not a replacement of limestone but an overgrowth of early-formed marine dolomite and pore-occluding cement. This study demonstrates that: (1) dolomite precipitated from a 75% seawater mixing-zone fluid that was both calcite saturated and sulfate-rich, and (2) dramatic textural maturation and stabilization in dolomite can occur in the near surface environment, without elevated temperature and burial conditions.

  14. 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

  15. Characteristics of the reaction zone in a combustor operating at mild combustion

    NASA Astrophysics Data System (ADS)

    Özdemir, İ. B.; Peters, N.

    stretching rates of the large structures. However, the flue gases entrained up to this point increased the inert content of the fresh mixture with chemical time scales comparable to the time scales of the flow. This allowed the reactants to attain temperatures near to those of the flue gases and to ignite with a small temperature rise, which led to a much lower thermal NO formation. The results also showed that when the equivalence ratio of the non- premixed mixtures was increased, the region where the combustion took place was shifted away from the burner and extended further downstream towards the roof. In the case of premixed combustion, however, the reaction started and terminated earlier and was confined to regions in close proximity to the axis. The emissions of OH radical occurred rather patchily and in relatively high concentrations.

  16. Formation of N-nitrosodimethylamine (NDMA) from reaction of monochloramine: a new disinfection by-product.

    PubMed

    Choi, Junghoon; Valentine, Richard L

    2002-02-01

    Studies have been conducted specifically to investigate the hypothesis that N-nitrosodimethylamine (NDMA) can be produced by reactions involving monochloramine. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed from the reaction between DMA and monochloramine indicating that it should be considered a potential disinfection by-product. The formation of NDMA increased with increased monochloramine concentration and showed maximum in yield when DMA was varied at fixed monochloramine concentrations. The mass spectra of the NDMA formed from DMA and 15N isotope labeled monochloramine (15NH2Cl) showed that the source of one of the nitrogen atoms in the nitroso group in NDMA was from monochloramine. Addition of 0.05 and 0.5 mM of preformed monochloramine to a secondarily treated wastewater at pH 7.2 also resulted in the formation of 3.6 and 111 ng/L of NDMA, respectively, showing that this is indeed an environmentally relevant NDMA formation pathway. The proposed NDMA formation mechanism consists of (i) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (ii) the oxidation of UDMH by monochloramine to NDMA, and (iii) the reversible chlorine transfer reaction between monochloramine and DMA which is parallel to (i). We conclude that reactions involving monochloramine in addition to classical nitrosation reactions are potentially important pathways for NDMA formation.

  17. EEG reactions of the human brain in the gradient magnetic field zone of the active geological fault (pilot study)

    NASA Astrophysics Data System (ADS)

    Pobachenko, S. V.; Shitov, A. V.; Grigorjev, P. E.; Sokolov, M. V.; Zubrilkin, A. I.; Vypiraylo, D. N.; Solovjev, A. V.

    2016-12-01

    This paper presents the results of experimental studies of the dynamics of the functional state of a person within the zone of an active geological fault characterized by abnormal spatial distribution of the magnetic- field vector values. It is shown that these geophysical modifications have a pronounced effect on the fluctuations of the electrical activity of the human brain. When the person gets into a zone with abnormal levels of gradient magnetic field in the absence of any subjective sensations, a nonspecific orientation activation reaction is observed, which is characterized by a significant increase in the levels of peak performance in key functional EEG frequency bands.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  19. Quasifission in heavy and superheavy element formation reactions

    NASA Astrophysics Data System (ADS)

    Hinde, D. J.; Dasgupta, M.; Jeung, D. Y.; Mohanto, G.; Prasad, E.; Simenel, C.; Walshe, J.; Wahkle, A.; Williams, E.; Carter, I. P.; Cook, K. J.; Kalkal, Sunil; Rafferty, D. C.; Rietz, R. du; Simpson, E. C.; David, H. M.; Düllmann, Ch. E.; Khuyagbaatar, J.

    2016-12-01

    Superheavy elements are created in the laboratory by the fusion of two heavy nuclei. The large Coulomb repulsion that makes superheavy elements decay also makes the fusion process that forms them very unlikely. Instead, after sticking together for a short time, the two nuclei usually come apart, in a process called quasifission. Mass-angle distributions give the most direct information on the characteristics and time scales of quasifission. A systematic study of carefully chosen mass-angle distributions has provided information on the global trends of quasifission. Large deviations from these systematics reveal the major role played by the nuclear structure of the two colliding nuclei in determining the reaction outcome, and thus implicitly in hindering or favouring superheavy element production.

  20. Modeling the formation and reactions of benzene metabolites.

    PubMed

    Golding, Bernard T; Barnes, Martine L; Bleasdale, Christine; Henderson, Alistair P; Jiang, Dong; Li, Xin; Mutlu, Esra; Petty, Hannah J; Sadeghi, Majid M

    2010-03-19

    One or more of the muconaldehyde isomers is a putative product of benzene metabolism. As muconaldehydes are highly reactive dienals and potentially mutagenic they might be relevant to the carcinogenicity of benzene. Muconaldehydes may be derived through the action of a cytochrome P450 mono-oxygenase on benzene oxide-oxepin, which are established metabolites of benzene. Oxidation of benzene oxide-oxepin either by the one-electron oxidant cerium(IV) ammonium nitrate (CAN) or by iron(III) tris(1,10-phenanthroline) hexafluorophosphate in acetone at -78 degrees C or acetonitrile at -40 degrees C gave (E,Z)-muconaldehyde, which was a single diastereoisomer according to analysis by (1)H NMR spectroscopy. Reaction of toluene-1,2-oxide/2-methyloxepin with CAN gave (2E,4Z)-6-oxo-hepta-2,4-dienal. Similarly, the action of CAN on 1,6-dimethylbenzene oxide-2,7-dimethyloxepin gave (3Z,5E)-octa-3,5-diene-2,7-dione. In vivo, benzene oxide-oxepin could suffer one-electron oxidation by cytochrome P450 mono-oxygenase giving (E,Z)-muconaldehyde. The observations presented may be relevant to the toxicology of benzene oxide-oxepin and other arene oxide-oxepins as we have previously shown that (E,Z)-muconaldehyde, analogously to (Z,Z)-muconaldehyde, affords pyrrole adducts with the exocyclic amino groups of the DNA bases adenine and guanine. Independent of their possible toxicological significance, the experiments described provide preparatively useful routes to (E,Z)-muconaldehyde and its congeners. Methods are also described for the trapping and analysis of reactive benzene metabolites, e.g. using the Diels-Alder reaction with the dienophile 4-phenyl-1,2,4-triazoline-3,5-dione to trap arene oxides and with the diene 1,3-diphenylisobenzofuran to trap enals.

  1. INSIDE-OUT PLANET FORMATION. III. PLANET–DISK INTERACTION AT THE DEAD ZONE INNER BOUNDARY

    SciTech Connect

    Hu, Xiao; Tan, Jonathan C.; Chatterjee, Sourav; Zhu, Zhaohuan

    2016-01-01

    The Kepler mission has discovered more than 4000 exoplanet candidates. Many of them are in systems with tightly packed inner planets. Inside-out planet formation (IOPF) has been proposed as a scenario to explain these systems. It involves sequential in situ planet formation at the local pressure maximum of a retreating dead zone inner boundary (DZIB). Pebbles accumulate at this pressure trap, which builds up a pebble ring and then a planet. The planet is expected to grow in mass until it opens a gap, which helps to both truncate pebble accretion and also induce DZIB retreat that sets the location of formation of the next planet. This simple scenario may be modified if the planet undergoes significant migration from its formation location. Thus, planet–disk interactions play a crucial role in the IOPF scenario. Here we present numerical simulations that first assess the degree of migration for planets of various masses that are forming at the DZIB of an active accretion disk, where the effective viscosity is undergoing a rapid increase in the radially inward direction. We find that torques exerted on the planet by the disk tend to trap the planet at a location very close to the initial pressure maximum where it formed. We then study gap opening by these planets to assess at what mass a significant gap is created. Finally, we present a simple model for DZIB retreat due to penetration of X-rays from the star to the disk midplane. Overall, these simulations help to quantify both the mass scale of first (“Vulcan”) planet formation and the orbital separation to the location of second planet formation.

  2. Inside-out Planet Formation. III. Planet-Disk Interaction at the Dead Zone Inner Boundary

    NASA Astrophysics Data System (ADS)

    Hu, Xiao; Zhu, Zhaohuan; Tan, Jonathan C.; Chatterjee, Sourav

    2016-01-01

    The Kepler mission has discovered more than 4000 exoplanet candidates. Many of them are in systems with tightly packed inner planets. Inside-out planet formation (IOPF) has been proposed as a scenario to explain these systems. It involves sequential in situ planet formation at the local pressure maximum of a retreating dead zone inner boundary (DZIB). Pebbles accumulate at this pressure trap, which builds up a pebble ring and then a planet. The planet is expected to grow in mass until it opens a gap, which helps to both truncate pebble accretion and also induce DZIB retreat that sets the location of formation of the next planet. This simple scenario may be modified if the planet undergoes significant migration from its formation location. Thus, planet-disk interactions play a crucial role in the IOPF scenario. Here we present numerical simulations that first assess the degree of migration for planets of various masses that are forming at the DZIB of an active accretion disk, where the effective viscosity is undergoing a rapid increase in the radially inward direction. We find that torques exerted on the planet by the disk tend to trap the planet at a location very close to the initial pressure maximum where it formed. We then study gap opening by these planets to assess at what mass a significant gap is created. Finally, we present a simple model for DZIB retreat due to penetration of X-rays from the star to the disk midplane. Overall, these simulations help to quantify both the mass scale of first (“Vulcan”) planet formation and the orbital separation to the location of second planet formation.

  3. 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.

  4. Nickel-Catalyzed Reactions Directed toward the Formation of Heterocycles.

    PubMed

    Kurahashi, Takuya; Matsubara, Seijiro

    2015-06-16

    Heterocycles have garnered significant attention because they are important functional building blocks in various useful molecules, such as pharmaceuticals, agricultural chemicals, pesticides, and materials. Several studies have been conducted regarding the preparation of heterocyclic skeletons with an emphasis on selectivity and efficiency. Three strategies are typically employed to construct cyclic molecules, namely, cyclization, cycloaddition, and ring-size alterations. Although each method has certain advantages, cycloaddition may be superior from the viewpoint of divergence. Specifically, cycloadditions enable the construction of rings from several pieces. However, the construction of heterocycles via cycloadditions is more challenging than the construction of carbocycles. For heterocycle construction, simple pericyclic reactions rarely work smoothly because of the large HOMO-LUMO gap unless well-designed combinations, such as electron-rich dienes and aldehydes, are utilized. Thus, a different approach should be employed to prepare heterocycles via cycloadditions. To this end, the use of metallacycles containing heteroatoms is expected to serve as a promising solution. In this study, we focused on the preparation of heteroatom-containing nickelacycles. Because nickel possesses a relatively high redox potential and an affinity for heteroatoms, several methods were developed to synthesize heteronickelacycles from various starting materials. The prepared nickelacycles were demonstrated to be reasonable intermediates in cycloaddition reactions, which were used to prepare various heterocycles. In this Account, we introduce the following four methods to prepare heterocycles via heteronickelacycles. (1) Direct oxidative insertion of Ni(0) to α,β-unsaturated enone derivatives: treatment of 3-ethoxycarbonyl-4-phenyl-3-buten-2-one with Ni(0) afforded an oxa-nickelacycle, which reacted with alkynes to give pyrans. (2) Substitution of a part of a cyclic compound with

  5. Phosphorus Zoning Patterns and the Formation of Olivine-Hosted Melt Inclusions

    NASA Astrophysics Data System (ADS)

    Milman-Barris, M. S.; Baker, M.; Beckett, J.; Sobolev, A.; Vielzeuf, D.; Stolper, E.

    2006-12-01

    composition produced ol (to ~2 mm in size) with coupled zoning of P, Al, and Cr; some show oscillatory or sector-zoning. Nearly all experimental ol grains have embayments and interior melt pools (up to 1 mm in longest dimension). While many of these are likely in contact with far-field melt, some may be isolated (i.e., true inclusions). Interior melt pools have aspect ratios of 1-40; the more elongate pools are similar in appearance to those of [3]. Enclosed, interior melt pools are surrounded by P-poor ol, but near P-rich ol. Also, boundaries between high- and low-P zones are often deflected in the vicinity of melt pools. These observations are reminiscent of inclusions observed in Hawaiian ol phenocrysts. Our experiments show that P-zoning in ol and associated interior melt pools can be produced by simple linear cooling histories. The proximity of melt inclusions to P-rich zones in both Hawaiian and experimental ol points to the importance of rapid growth in the formation of both features. Cross-cutting (and perhaps replacement) of high-P features in ol by the low-P zones surrounding natural melt inclusions may reflect trapping of melt inclusions in pits formed by localized dissolution of growing ol, recrystallization of high-energy ol adjacent to melt inclusions after trapping, and/or melting/reprecipitation of ol adjacent to trapped melt inclusions due to transient thermal gradients. [1] Sobolev et al. (2000) Nature 404, 986-990. [2] Norman et al. (2002) Chem. Geol. 183, 143-68. [3] Faure &Schiano (2005) EPSL 236, 882-98.

  6. 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

  7. 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.

  8. 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.

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

    PubMed

    Sinha, Sourab; Raj, Abhijeet

    2016-03-21

    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.

  10. A comparison of models describing residual NAPL formation in the vadose zone

    SciTech Connect

    Oostrom, Mart; White, Mark D.; Lenhard, Robert J.; Van Geel, Paul; Wietsma, Thomas W.

    2005-02-01

    A major shortcoming of multifluid flow simulators is the inability to predict the retention of nonaqueous phase liquid (NAPL) in the vadose zone after long drainage periods. Recently, three theoretical models, Wipfler and Van Der Zee [J. Contam. Hydrol. 50 (2001); WVDZ model], Van Geel and Roy [J. Contam. Hydrol. 58 (2002); VGR model], and Lenhard et al. [J. Contam. Hydrol. (2004) In Press; LOD model] have been proposed for describing residual NAPL formation. The WVDZ model assumes a critical total liquid saturation below which all NAPL becomes residual. The VGR and LOD models are extensions of an existing hysteretic relative permeability ''saturation'' capillary pressure model and assume formation of residual NAPL during NAPL drainage and imbibition, respectively. In this paper, we compare model predictions against results of a series of static pressure cell experiments. We found no experimental evidence supporting the WVDZ concept of a critical total liquid saturation. The other two models yielded reasonable predictions. The VGR and LOD models were then incorporated into a multifluid flow simulator and simulations of two transient column experiments were conducted. Both models performed considerably better than simulations without considering the formation of residual NAPL, underwriting the importance of incorporating this process in simulators. Although the VGR and LOD models are based on different conceptual models, no clear performance differences could be observed when simulation results were compared against the transient experimental data.

  11. Kinetic study of model reactions in the gas phase at the early stage of coke formation

    SciTech Connect

    Nohara, D.; Sakai, T. )

    1992-01-01

    This paper reports that the most probable gas-phase reactions at the early stage of coke formation were elucidated by kinetic study on the model reactions adopted for formation of cyclic compounds and growth of ring. It was revealed that the formation and growth of ring proceeded mainly through cycloaddition of butadiene or allyl radicals to unsaturated hydrocarbons at relatively low temperatures ({approximately}600{degrees}C), i.e., through a Diels-Alder type reaction. On the other hand, such growth of ring as formation of biphenyl accompanying dehydrogenation from benzene can proceed only at the higher temperatures. It was also revealed that in the growth of the ring, cycloaddition of butadiene favors a cyclic olefin molecule that possesses a nonconjugated double bond and a nearly planar structure.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Heterotrimeric Kinesin-2 (KIF3) Mediates Transition Zone and Axoneme Formation of Mouse Photoreceptors*

    PubMed Central

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

    2015-01-01

    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 embKif3a−/− and in embIft88−/− mice, basal bodies failed to extend transition zones (connecting cilia) with outer segments, and visual pigments mistrafficked. In contrast, tamKif3a−/− and tamIft88−/− 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

  17. 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. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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

    PubMed

    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.

  19. 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

  20. 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.

  1. Planetesimal formation via sweep-up growth at the inner edge of dead zones

    NASA Astrophysics Data System (ADS)

    Drążkowska, J.; Windmark, F.; Dullemond, C. P.

    2013-08-01

    Context. The early stages of planet formation are still not well understood. Coagulation models have revealed numerous obstacles to the dust growth, such as the bouncing, fragmentation, and radial drift barriers. Gas drag causes rapid loss, and turbulence leads to generally destructive collisions between the dust aggregates. Aims: We study the interplay between dust coagulation and drift to determine the conditions in protoplanetary disk that support the formation of planetesimals. We focus on planetesimal formation via sweep-up and investigate whether it can take place in a realistic protoplanetary disk. Methods: We have developed a new numerical model that resolves the spatial distribution of dust in the radial and vertical dimensions. The model uses representative particles approach to follow the dust evolution in a protoplanetary disk. The coagulation and fragmentation of solids is taken into account in the Monte Carlo method. A collision model adopting the mass transfer effect, which can occur for different-sized dust aggregate collisions, is implemented. We focus on a protoplanetary disk that includes a pressure bump caused by a steep decline of turbulent viscosity around the snow line. Results: Our results show that high enough resolution of the vertical disk structure in dust coagulation codes is needed to obtain adequately short growth timescales, especially in the case of a low turbulence region. We find that a sharp radial variation in the turbulence strength at the inner edge of dead zone promotes planetesimal formation in several ways. It provides a pressure bump that efficiently prevents the dust from drifting inwards. It also causes a radial variation in the size of aggregates at which growth barriers occur, favoring the growth of large aggregates by sweeping up of small particles. In our model, by employing an ad hoc α viscosity change near the snow line, it is possible to grow planetesimals by incremental growth on timescales of approximately 105

  2. 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

  3. 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.

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

    PubMed Central

    2013-01-01

    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. PMID:23614645

  5. Computational study of peptide bond formation in the gas phase through ion-molecule reactions.

    PubMed

    Redondo, Pilar; Martínez, Henar; Cimas, Alvaro; Barrientos, Carmen; Largo, Antonio

    2013-08-21

    A computational study of peptide bond formation from gas-phase ion-molecule reactions has been carried out. We have considered the reaction between protonated glycine and neutral glycine, as well as the reaction between two neutral glycine molecules for comparison purposes. Two different mechanisms, concerted and stepwise, were studied. Both mechanisms show significant energy barriers for the neutral reaction. The energy requirements for peptide bond formation are considerably reduced upon protonation of one of the glycine molecules. For the reaction between neutral glycine and N-protonated glycine the lowest energy barrier is observed for the concerted mechanism. For the reaction between neutral glycine and protonated glycine at carbonyl oxygen, the preferred mechanism is the stepwise one, with a relatively small energy barrier (23 kJ mol(-1) at 0 K) and leading to the lowest-lying protonated glycylglycine isomer. In the case that the reaction could be initiated by protonated glycine at hydroxyl oxygen the process would be barrier-free and clearly exothermic. In that case peptide bond formation could take place even under interstellar conditions if glycine is present in space.

  6. Formation of HCN+ in heterogeneous reactions of N2(+) and N+ with surface hydrocarbons.

    PubMed

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

    2013-10-03

    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 10(4) collisions with the surfaces.

  7. 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.

  8. 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.

  9. 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.

  10. Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule.

    PubMed

    Tsai, Po-Yu; Che, Dock-Chil; Nakamura, Masaaki; Lin, King-Chuen; Kasai, Toshio

    2011-01-28

    The orientation dependence of Br-atom formation in the reaction of the oriented OH radical with the HBr molecule using the hexapole electrostatic field was studied. Experimental results for the orientation dependence in the reaction were analyzed using a Legendre polynomial fit. The results show two reactive sites. It was found that O-end attack is most favored for this reaction, and that H-end attack also shows a pronounced reactivity. The reactivity of the side-ways attack was found to be small. By comparing the results of the orientation dependence in the reaction with studies of inelastic collisions and theoretical calculations, two reaction pathways are proposed. Reaction by O-end attack is followed by a direct abstraction of the H-atom from the HBr molecule. The mechanism for H-end attack may have H-atom migration from HBr to form the water molecule.

  11. 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

  12. 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

  13. Secondary Organic Aerosol Formation by Molecular-Weight Building Reactions of Biogenic Oxidation Products

    NASA Astrophysics Data System (ADS)

    Barsanti, K.; Guenther, A.; Matsunaga, S.; Smith, J.

    2006-12-01

    Understanding the chemical composition of atmospheric organic aerosols (OA) remains one of the significant challenges to accurately representing OA in air quality and climate models. Meeting this challenge will require further understanding of secondary organic aerosols (SOA), of which biogenic emissions are thought to be major precursors. Of recent interest is the significance of higher-molecular weight (MW) compounds (i.e., "oligomers"). Theoretical, laboratory, and field study results suggest that relatively volatile oxidation products may contribute to SOA formation through multi-phase MW- building reactions. The significance of such reactions for biogenic SOA formation, including for newly considered precursors such as isoprene, is explored in this work. Theoretical and field studies are employed to: 1) identify MW-building reactions that may contribute to SOA formation in the atmosphere, 2) identify MW-building reaction products in ambient samples, and 3) parameterize atmospheric SOA formation by MW-building reactions of biogenic oxidation products. Likely reactions of biogenic oxidation products include ester, amide, and peroxyhemiacetal formation. Each of the proposed reactions involves known oxidation productions of biogenic precursors (e.g., carboxylic acids and aldehydes) reacting with one another and/or other atmospheric constituents (e.g., sulfuric acid and ammonia) to form higher-MW/lower-volatility products that can condense to form SOA. It has been suggested that products of MW-building reactions can revert to the parent reactants during sampling and analysis. Thus, relatively volatile compounds detected in ambient particle samples in fact may be decomposition products of higher-MW products. The contribution of relatively volatile biogenic oxidation products to SOA via ester, amide, and peroxyhemiacetal formation, as determined by studies based on fundamental thermodynamics and gas/particle partitioning theory, will be discussed; in addition to

  14. 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.

  15. Deposition of a Jurassic ooid sand shoal - Smackover A zone of Buckner Formation, Corney Bayou field, Union Parish, Louisiana

    SciTech Connect

    Tye, E.N.; Moore, C.H.

    1986-09-01

    The Smackover A zone of the Buckner Formation in northern Louisiana and southern Arkansas is lithologically similar to the more thoroughly studied upper Smackover Formation. However, in contrast to the regionally occurring thick, blanket-like ooid sands of the upper Smackover, the Smackover A zone carbonates occur as strike-parallel, individual carbonate sand bodies isolated within the clays, muds, and evaporites of the upper Buckner. This isolation and its potential effects on fluid movement, diagenetic processes, and ultimate porosity evolution in similar sequences across northern Louisiana and southern Arkansas emphasize the importance of a well-constrained core-based field study.

  16. Iron nitrosyl hemoglobin formation from the reaction of hydroxylamine and hemoglobin under physiological conditions.

    PubMed

    Lockamy, Virginia L; Shields, Howard; Kim-Shapiro, Daniel B; King, S Bruce

    2004-11-01

    Sickle cell disease patients receiving hydroxyurea (HU) therapy have shown increases in the production of nitric oxide (NO) metabolites, which include iron nitrosyl hemoglobin (HbNO), nitrite, and nitrate. However, the exact mechanism by which HU forms HbNO in vivo is not understood. Previous studies indicate that the reaction of oxyhemoglobin (oxyHb) or deoxyhemoglobin (deoxyHb) with HU are too slow to account for in vivo HbNO production. In this study, we show that the reaction of methemoglobin (metHb) with HU to form HbNO could potentially be fast enough to account for in vivo HbNO formation but competing reactions of either excess oxyHb or deoxyHb during the reaction reduces the likelihood that HbNO will be produced from the metHb-HU reaction. Using electron paramagnetic resonance (EPR) spectroscopy we have detected measurable amounts of HbNO and metHb during the reactions of oxyHb, deoxyHb, and metHb with excess hydroxylamine (HA). We also demonstrate HbNO and metHb formation from the reactions of excess oxyHb, deoxyHb, or metHb and HA, conditions that are more likely to mimic those in vivo. These results indicate that the reaction of hydroxylamine with hemoglobin produces HbNO and lend chemical support for a potential role for hydroxylamine in the in vivo metabolism of hydroxyurea.

  17. Secondary organic aerosol formation from reaction of tertiary amines with nitrate radical

    NASA Astrophysics Data System (ADS)

    Erupe, M. E.; Price, D. J.; Silva, P. J.; Malloy, Q. G. J.; Qi, L.; Warren, B.; Cocker, D. R., III

    2008-09-01

    Secondary organic aerosol formation from the reaction of tertiary amines with nitrate radical was investigated in an indoor environmental chamber. Particle chemistry was monitored using a high resolution aerosol mass spectrometer while gas-phase species were detected using a proton transfer reaction mass spectrometer. Trimethylamine, triethylamine and tributylamine were studied. Results indicate that tributylamine forms the most aerosol mass followed by trimethylamine and triethylamine respectively. Spectra from the aerosol mass spectrometer indicate the formation of complex non-salt aerosol products. We propose a reaction mechanism that proceeds via abstraction of a proton by nitrate radical followed by RO2 chemistry. Rearrangement of the aminyl alkoxy radical through hydrogen shift leads to the formation of hydroxylated amides, which explain most of the higher mass ions in the mass spectra. These experiments show that oxidation of tertiary amines by nitrate radical may be an important night-time source of secondary organic aerosol.

  18. Optimized Reaction Conditions for Amide Bond Formation in DNA-Encoded Combinatorial Libraries.

    PubMed

    Li, Yizhou; Gabriele, Elena; Samain, Florent; Favalli, Nicholas; Sladojevich, Filippo; Scheuermann, Jörg; Neri, Dario

    2016-08-08

    DNA-encoded combinatorial libraries are increasingly being used as tools for the discovery of small organic binding molecules to proteins of biological or pharmaceutical interest. In the majority of cases, synthetic procedures for the formation of DNA-encoded combinatorial libraries incorporate at least one step of amide bond formation between amino-modified DNA and a carboxylic acid. We investigated reaction conditions and established a methodology by using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide, 1-hydroxy-7-azabenzotriazole and N,N'-diisopropylethylamine (EDC/HOAt/DIPEA) in combination, which provided conversions greater than 75% for 423/543 (78%) of the carboxylic acids tested. These reaction conditions were efficient with a variety of primary and secondary amines, as well as with various types of amino-modified oligonucleotides. The reaction conditions, which also worked efficiently over a broad range of DNA concentrations and reaction scales, should facilitate the synthesis of novel DNA-encoded combinatorial libraries.

  19. The formation of Uranus and Neptune in solid-rich feeding zones: Connecting chemistry and dynamics

    NASA Astrophysics Data System (ADS)

    Dodson-Robinson, Sarah E.; Bodenheimer, Peter

    2010-05-01

    The core accretion theory of planet formation has at least two fundamental problems explaining the origins of Uranus and Neptune: (1) dynamical times in the trans-saturnian solar nebula are so long that core growth can take >15 Myr and (2) the onset of runaway gas accretion that begins when cores reach ˜10 M⊕ necessitates a sudden gas accretion cutoff just as Uranus and Neptune's cores reach critical mass. Both problems may be resolved by allowing the ice giants to migrate outward after their formation in solid-rich feeding zones with planetesimal surface densities well above the minimum-mass solar nebula. We present new simulations of the formation of Uranus and Neptune in the solid-rich disk of Dodson-Robinson et al. (Dodson-Robinson, S.E., Willacy, K., Bodenheimer, P., Turner, N.J., Beichman, C.A. [2009]. Icarus 200, 672-693) using the initial semimajor axis distribution of the Nice model (Gomes, R., Levison, H.F., Tsiganis, K., Morbidelli, A. [2005]. Nature 435, 466-469; Morbidelli, A., Levison, H.F., Tsiganis, K., Gomes, R. [2005]. Nature 435, 462-465; Tsiganis, K., Gomes, R., Morbidelli, A., Levison, H.F. [2005]. Nature 435, 459-461), with one ice giant forming at 12 AU and the other at 15 AU. The innermost ice giant reaches its present mass after 3.8-4.0 Myr and the outermost after 5.3-6 Myr, a considerable time decrease from previous one-dimensional simulations (e.g. Pollack, J.B., Hubickyj, O., Bodenheimer, P., Lissauer, J.J., Podolak, M., Greenzweig, Y. [1996]. Icarus 124, 62-85). The core masses stay subcritical, eliminating the need for a sudden gas accretion cutoff. Our calculated carbon mass fractions of 22% are in excellent agreement with the ice giant interior models of Podolak et al. (Podolak, M., Weizman, A., Marley, M. [1995]. Planet. Space Sci. 43, 1517-1522) and Marley et al. (Marley, M.S., Gómez, P., Podolak, M. [1995]. J. Geophys. Res. 100, 23349-23354). Based on the requirement that the ice giant-forming planetesimals contain >10% mass

  20. Tectonic Activity and Processes Preceding the Formation of the Dead Sea Fault Zone

    NASA Astrophysics Data System (ADS)

    Eppelbaum, L. V.; Pilchin, A. N.

    2007-12-01

    Analysis of geological-geophysical data indicates that at the end of the Proterozoic, blocks of the Arabian Shield (AS) were thrust to the north-west onto the crust of the proto-Mediterranean (PM). This was caused by the pushing of oceanic crust from the south-east forming the Najd faults system (NF). This thrusting took place between 630 and 590 Ma, and is confirmed by the offsets between the Yanbu suture of the AS and Allaqi-Sol Hamid suture of the Nubian Shield (NS), the Bi'r Umq suture of AS and Nakasib suture of NS, and parts of the Yanbu and Nabitah sutures of AS. This caused the separation of AS from NS, and AS from the continental crust to north-east of it with its north-western displacement, resulting in opening of the Persian Gulf. This caused the start of deposition of huge amounts of Vendian-Cambrian evaporites in Saudi Arabia, Oman, Persian Gulf, Zagros, central Iran and other regions. The fact of the formation and preservation of the evaporites, and the common similarities in Vendian-Triassic sedimentary cover of Central Iran, Zagros, Taurus, and Arabian Plate (AP) and common Late Proterozoic-Early Paleozioc magmatic activity, show that these regions did not change their position significantly since then. Results of the DESERT project show that the lowermost part of the crust is present east of the Dead Sea Fault Zone (DSFZ), but it is absent west of it. This could be explained by detachment of the bottom part of the crust west of DSFZ during AP thrusting onto the crust of PM. The lithospheric slice discovered by seismic data between Moho and depth of about 55 km in S. Israel could be a remnant of that crust. During the thrusting, the AP overrode the detached slice. The slice was later remelted during formation of the postorogenic magmatic rocks of 590-530 Ma widespread in Jordan. The formation of three dyke swarms in S. Israel (600-540 Ma), widespread dykes in Sinai (590-530 Ma) and AP (590-530 Ma), as well as high-T-low-P metamorphism between 600

  1. Coordinated trafficking of synaptic vesicle and active zone proteins prior to synapse formation.

    PubMed

    Bury, Luke A D; Sabo, Shasta L

    2011-05-10

    The proteins required for synaptic transmission are rapidly assembled at nascent synapses, but the mechanisms through which these proteins are delivered to developing presynaptic terminals are not understood. Prior to synapse formation, active zone proteins and synaptic vesicle proteins are transported along axons in distinct organelles referred to as piccolo-bassoon transport vesicles (PTVs) and synaptic vesicle protein transport vesicles (STVs), respectively. Although both PTVs and STVs are recruited to the same site in the axon, often within minutes of axo-dendritic contact, it is not known whether or how PTV and STV trafficking is coordinated before synapse formation. Here, using time-lapse confocal imaging of the dynamics of PTVs and STVs in the same axon, we show that vesicle trafficking is coordinated through at least two mechanisms. First, a significant proportion of STVs and PTVs are transported together before forming a stable terminal. Second, individual PTVs and STVs share pause sites within the axon. Importantly, for both STVs and PTVs, encountering the other type of vesicle increases their propensity to pause. To determine if PTV-STV interactions are important for pausing, PTV density was reduced in axons by expression of a dominant negative construct corresponding to the syntaxin binding domain of syntabulin, which links PTVs with their KIF5B motor. This reduction in PTVs had a minimal effect on STV pausing and movement, suggesting that an interaction between STVs and PTVs is not responsible for enhancing STV pausing. Our results indicate that trafficking of STVs and PTVs is coordinated even prior to synapse development. This novel coordination of transport and pausing might provide mechanisms through which all of the components of a presynaptic terminal can be rapidly accumulated at sites of synapse formation.

  2. Implications of Shear Heating and Fracture Zones for Ridge Formation on Europa

    NASA Astrophysics Data System (ADS)

    Han, Lijie; Showman, A. P.

    2007-10-01

    Ridges are ubiquitous on Europa; parts of the satellite are covered solely by multiple generations of overprinted ridge pairs. Typically, ridges are 100-300 m in height, a few kilometers in width, and contain a central trough. Many ridge-formation scenarios have been suggested, including runaway frictional heating along fractures, which causes a temperature increase and leads to buoyant uplift along the fracture. Here we present 2D and 3D numerical simulations of ice-shell convection to test the role of shear heating and weakening by fractures on Europan ridge formation. We used the finite-element codes ConMan and CitCom to solve the equations governing thermal convection in Europa's ice shell in two- and three- dimensional Cartesian geometry. Our simulations show that a pre-existing fracture zone promotes upwelling and lithospheric thinning, leading to topographic uplift of 50 m; although promising, this is insufficient to explain the topography of Europan ridges. Shear heating also promotes lithospheric thinning and buoyant ascent, producing a linear feature with topography up to 120 m. Topography remains linear along strike even under the influence of heterogeneous 3D convection within the ice shell. Our simulated topography broadly resembles that of Europan ridges, including (in most simulations) the shallow marginal troughs on either side of the ridge, although the central trough is not reproduced. Despite this deficiency, our simulations support the idea that shear heating can produce Europa's ridges. Although the simulations presented here assumed a pure-ice composition, compositional effects could play an important role in ridge formation, and these effects will be considered in a future study.

  3. 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.

  4. [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.

  5. 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.

  6. A multiphysics model of in vitro transcription coupling enzymatic reaction and precipitation formation.

    PubMed

    Akama, Satoru; Yamamura, Masayuki; Kigawa, Takanori

    2012-01-18

    Multiphysics modeling, which integrates the models studied in different disciplines so far, is an indispensable approach toward a comprehensive understanding of biological systems composed of diverse phenomena. However, the variety of the models is narrower than the actual diverse phenomena because of the difficulty in coupling independent models separately studied in different disciplines for the actual coupled phenomena. In this study, we develop a mathematical model coupling an enzymatic reaction and mineralization formation. As a test case, we selected an in vitro transcription system where a transcription reaction occurs along with the precipitation formation of magnesium pyrophosphate (Mg(2)PPi). To begin, we experimentally elucidated how the transcription reaction and the precipitation formation are coupled. In the analysis, we applied a Michaelis-Menten-type equation to the transcription reaction and a semiempirical equation describing the correlation between the induction period and the supersaturation ratio to the precipitation formation, respectively. Based on the experimental results, we then integrated these two models. These models were connected by supersaturation that increases as the transcription reaction proceeds and becomes the driving force of the precipitation. We believe that our modeling approach could significantly contribute to the development of newer multiphysics models in systems biology such as bone metabolic networks. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  7. A Multiphysics Model of In Vitro Transcription Coupling Enzymatic Reaction and Precipitation Formation

    PubMed Central

    Akama, Satoru; Yamamura, Masayuki; Kigawa, Takanori

    2012-01-01

    Multiphysics modeling, which integrates the models studied in different disciplines so far, is an indispensable approach toward a comprehensive understanding of biological systems composed of diverse phenomena. However, the variety of the models is narrower than the actual diverse phenomena because of the difficulty in coupling independent models separately studied in different disciplines for the actual coupled phenomena. In this study, we develop a mathematical model coupling an enzymatic reaction and mineralization formation. As a test case, we selected an in vitro transcription system where a transcription reaction occurs along with the precipitation formation of magnesium pyrophosphate (Mg2PPi). To begin, we experimentally elucidated how the transcription reaction and the precipitation formation are coupled. In the analysis, we applied a Michaelis-Menten-type equation to the transcription reaction and a semiempirical equation describing the correlation between the induction period and the supersaturation ratio to the precipitation formation, respectively. Based on the experimental results, we then integrated these two models. These models were connected by supersaturation that increases as the transcription reaction proceeds and becomes the driving force of the precipitation. We believe that our modeling approach could significantly contribute to the development of newer multiphysics models in systems biology such as bone metabolic networks. PMID:22339858

  8. 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.

  9. Formation and transport of deethylatrazine in the soil and vadose zone

    USGS Publications Warehouse

    Adams, C.D.; Thurman, E.M.

    1991-01-01

    Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and two degradation products were monitored at seven depths in the soil and vadose zone throughout the growing season in two experimental plots in which corn (Zea mays L.) was grown. The soils in these plots were a Kimo silty clay loam (clayey over loamy, montmorillonitic, mesic, Fluvaquentic Hapludoll) and a Eudora silt loam (course, silty, mixed, mesic, Fluventic Hapludoll). The purpose this field study was to identify and quantify the mobile and persistent degradation products of atrazine that comprise the input, or “source term,” to groundwater resulting from the application of atrazine to the soils. The formation of deethylatrazine (2-amino-4-chloro-6-isopropylamino-s-triazine) and deisopropylatrazine (2-amino-4-chloro-6-ethylamino-s-triazine) was monitored at vurious depths using suction lysimeters to determine the relative proportions at which these compounds enter the aquifer. Deethylatrazine was the major degradation product of atrazine identified in the soil water and appeared to enter the underlying aquifer at a concentration of 5.0 µg/L, which was greater than the concentration of atrazine entering the aquifer. Deisopropylatrazine also was detected in the soil water, bnt only in minor concentrations relative to atrazine and deethylatrazine. Because deethylatrazine was the major degradation product in the unsaturated zone, the deethylatrazine-to-atrazine ratio (DAR) may be a good indicator of transport of atrazine through the soil. The hypothesis is proposed that the DAR may be used to distinguish point-source from nonpoint-source contamination of an aquifer.

  10. Towards a multi-scale understanding of the gas-star formation cycle in the Central Molecular Zone

    NASA Astrophysics Data System (ADS)

    Kruijssen, J. M. Diederik

    2017-01-01

    The Central Molecular Zone (CMZ, the central 500 pc of the Milky Way) contains the largest reservoir of high-density molecular gas in the Galaxy, but forms stars at a rate 10-100 times below commonly-used star formation relations. We discuss recent efforts in understanding how the nearest galactic nucleus forms its stars. The latest models of the gas inflow, star formation, and feedback duty cycle reproduce the main observable features of the CMZ, showing that star formation is episodic and that the CMZ currently resides at a star formation minimum. Using orbital modelling, we derive the three-dimensional geometry of the CMZ and show how the orbital dynamics and the star formation potential of the gas are closely coupled. We discuss how this coupling reveals the physics of star formation and feedback under the conditions seen in high-redshift galaxies, and promotes the formation of the densest stellar clusters in the Galaxy.

  11. Ecohydrological Consequences of Critical Zone Structure in the Franciscan Formation, Northern California Coast Ranges

    NASA Astrophysics Data System (ADS)

    Hahm, W. J.; Dietrich, W. E.; Dawson, T. E.; Lovill, S.; Rempe, D.

    2016-12-01

    Water availability regulates ecosystem function, particularly in seasonally dry climates where lack of moisture in the growing season acts as an ecological bottleneck. Water within hillslopes is extracted by plants during transpiration and also delivered to streams to support baseflow for riparian ecosystems and human use. How water is stored and then released from hillslopes is strongly influenced by the structure of the critical zone (CZ) that emerges from the complex interaction of lithology, climate, and tectonics. Here we show how contrasting CZ development has extreme ecohydrological consequences in the seasonally dry climate of the Northern California Coast Ranges. To explore how the CZ transmits and stores water, we studied hydrologic dynamics at two sites with similar climate across belts of the Franciscan Formation in the Eel River CZO. We monitored plant water use, precipitation inputs and stream runoff, groundwater and vadose zone moisture dynamics and documented near-surface hydraulic conductivity and runoff-generation processes. We investigated CZ structure via boreholes and geophysical methods. We find that CZ thickness determines the extent to which hillslopes `shed' or `store' wet season precipitation, and fundamentally controls the structure of plant communities and summer low-flows. In a climate where winter precipitation regularly exceeds 2000 mm, the thin CZ of the sheared argillite matrix Central belt rapidly fills, resulting in wet-season saturation overland flow that drives flashy winter runoff in channels that then quickly run dry in the early summer. The maximum unsaturated moisture storage of approximately 200 mm is sufficient to host an ecologically diverse yet sparsely forested oak savanna. In contrast, the thick CZ of the interbedded argillite and greywacke Coastal belt stores up to 600 mm of winter precipitation in the unsaturated zone and a seasonal groundwater system within fractured bedrock provides year-round flow to channels

  12. 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.

  13. Paternò-Büchi reaction between furan and heterocyclic aldehydes: oxetane formation vs. metathesis.

    PubMed

    D'Auria, Maurizio; Racioppi, Rocco; Viggiani, Licia

    2010-08-01

    The photochemical reaction of 2-substituted heterocyclic aldehydes with furan gave the corresponding exo oxetane derivatives through the excited triplet state. However, in situ the oxetane derivatives were converted through a metathesis reaction into the corresponding Z,E-butadienyl formate derivatives. On the contrary, 3-substituted heterocyclic aldehydes gave the corresponding exo oxetane derivatives. The effect of 2-substituted heterocyclic ring in order to facilitate the metathesis reaction is explained considering the possible participation of the pi aromatic orbitals in the oxetane C-O bond cleavage.

  14. An alternative approach to aldol reactions: gold-catalyzed formation of boron enolates from alkynes.

    PubMed

    Körner, Cindy; Starkov, Pavel; Sheppard, Tom D

    2010-05-05

    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh(3)AuNTf(2) at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or intramolecular Chan-Lam coupling, respectively. A combined gold/boronic acid catalyzed aldol condensation reaction of an alkynyl aldehyde was also successfully achieved.

  15. 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.

  16. 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.

  17. Pattern formation driven by an acid-base neutralization reaction in aqueous media in a gravitational field.

    PubMed

    Zalts, A; El Hasi, C; Rubio, D; Ureña, A; D'Onofrio, A

    2008-01-01

    We report the hydrodynamic instabilities found in a simple exothermic neutralization reaction. Although the heavier aqueous NaOH solution was put below the lighter layer of aqueous HCl solution, fingering at the interface in a Hele-Shaw cell was observed. The reaction front, which propagates downward, becomes buoyantly unstable in the gravity field. The mixing zone length and wave number depend on the reactant concentrations. The mixing zone length increases and the wave number decreases when the reactant concentrations decrease.

  18. EXFOR systems manual: Nuclear reaction data exchange format. Revision 97/1

    SciTech Connect

    McLane, V.

    1997-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Center Network. 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 rather than optimization of data processing in order to meet the diverse needs of the nuclear reaction data centers. 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 exchange format, as outlined, is designed to allow 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).

  19. Contrasting MORB-Boninite melt reaction trends in IBM forearc moho transition zone

    NASA Astrophysics Data System (ADS)

    Loocke, M. P.; Snow, J. E.; Ishizuka, O.

    2013-12-01

    Models of arc crust formation prior to subduction initiation are hampered by a paucity of observations from present-day arc lower crust. Here we report petrographic analysis and mineral chemistry of spinel from 35 lower crustal peridotites and gabbros recovered from the inner trench slope of the Bonin Ridge (BR). Two groups of these gabbroic samples appear to have reacted with distinct melt compositions. Group M consists of peridotite (a single cpx-harzburgite), wehrlites, and gabbroic rocks with medium Cr# (100 x Cr / Cr + Al) spinels ranging from 45 to 60 and high TiO2 and Al2O3 spanning ~0.1-2.25 and ~12-30 wt. % respectively. Group B consists of only dunites and cpx-free peridotites with high Cr# spinels ranging from 65 to 94 and low TiO2 and Al2O3 spanning ~0-0.12 and ~3-21 wt. % respectively. The group M and group B samples appear to be the result of melt-rock reaction with a MORB-like melt and a more depleted boninitic melt respectively. MORB-like forearc basalts (FAB) (~50-52 Ma) and younger boninites (~44-48 Ma) recovered from the BR have been interpreted to represent a change from decompression melting at subduction initiation to flux melting and boninitic volcanism after establishment of the arc. The gabbroic samples of group M and group B similarly represent a lower crustal record of the change from MORB-like melts created by decompression melting at or soon after subduction initiation to arc-type flux melting and boninite volcanism thereafter. The presence of lower crustal peridotites and gabbroic rocks with spinels belonging to group M and not group B suggests that the lower crust of the BR may be dominated by gabbroic rocks and material genetically related to the FABs. This would imply that a large portion of the lower crust in the fore-arc was formed during or shortly after subduction initiation and is similar in composition to MOR lower crust.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Mass inventory of the giant-planet formation zone in a solar nebula analogue

    NASA Astrophysics Data System (ADS)

    Zhang, Ke; Bergin, Edwin A.; Blake, Geoffrey A.; Cleeves, L. Ilsedore; Schwarz, Kamber R.

    2017-06-01

    The initial mass distribution in the solar nebula is a critical input to planet formation models that seek to reproduce today's Solar System 1 . Traditionally, constraints on the gas mass distribution are derived from observations of the dust emission from disks 2,3 , but this approach suffers from large uncertainties in dust opacity and gas-to-dust ratio 2 . On the other hand, previous observations of gas tracers only probe surface layers above the bulk mass reservoir 4 . Here we present the first partially spatially resolved observations of the 13C18O J = 3-2 line emission in the closest protoplanetary disk, TW Hydrae, a gas tracer that probes the bulk mass distribution. Combining it with the C18O J = 3-2 emission and the previously detected HD J = 1-0 flux, we directly constrain the mid-plane temperature and optical depths of gas and dust emission. We report a gas mass distribution with radius, R, of 13 - 5 + 8 × ( R / 20 .5 au ) - 0.9 - 0.3 + 0.4  g cm-2 in the expected formation zone of gas and ice giants (5-21 au). We find that the mass ratio of total gas to millimetre-sized dust is 140 in this region, suggesting that at least 2.4M⊕ of dust aggregates have grown to centimetre sizes (and perhaps much larger). The radial distribution of gas mass is consistent with a self-similar viscous disk profile but much flatter than the posterior extrapolation of mass distribution in our own and extrasolar planetary systems.

  5. Modeling dichloroacetic acid formation from the reaction of monochloramine with natural organic matter.

    PubMed

    Duirk, Stephen E; Valentine, Richard L

    2006-08-01

    A kinetic model was developed to predict dichloroacetic acid (DCAA) formation in chloraminated systems. Equations describing DCAA formation were incorporated into an established comprehensive monochloramine-natural organic matter (NOM) reaction model. DCAA formation was theorized to be proportional to the amount of NOM oxidized by monochloramine and described by a single dimensionless DCAA formation coefficient, theta(DCAA) (M(DCAA)/M(DOC(ox)). The applicability of the model to describe DCAA formation in the presence of six different NOM sources was evaluated. DCAA formation could be described by considering a single NOM source-specific value for theta(DCAA) over a wide range of experimental conditions (i.e., pH, NOM, free ammonia, and monochloramine concentrations). DCAA formation appears to be directly proportional to the amount of active chlorine (monochloramine and free chlorine) that reacted with the NOM under these experimental conditions. Values of theta(DCAA) for all six NOM sources, determined by nonlinear regression analysis, varied from 6.51 x 10(-3) to 1.15 x 10(-2) and were linearly correlated with specific ultraviolet absorbance at 280 nm (SUVA(280)). The ability to model monochloramine loss and DCAA formation in the presence of NOM provides insight into disinfection by-product (DBP) formation pathways under chloramination conditions. The subsequent model and correlations to SUVA has the potential to aid the water treatment industry as a tool in developing strategies that minimize DBP formation while maintaining the microbial integrity of the water distribution system.

  6. The effects of phytic acid on the Maillard reaction and the formation of acrylamide.

    PubMed

    Wang, Huan; Zhou, Yamin; Ma, Jimei; Zhou, Yuanyuan; Jiang, Hong

    2013-11-01

    Phytic acid, myo-inositol hexaphosphoric acid, exists in substantial (1-5%) amounts in edible plant seeds. In this study the effects of phytic acid on the Maillard reaction and the formation of acrylamide were investigated. Both phytic acid and phosphate enhanced browning in glucose/β-alanine system, but phytic acid was less effective than phosphate. Higher pH favoured the catalytic activities for both of them. The influence of the types of sugar and amino acid on the reaction was also examined. Browning was suppressed by the addition of calcium and magnesium ions, but an additive effect was observed for ferrous ions and phytic acid in glucose/β-alanine solution at pH 8.0. Both phytic acid and phosphate promoted the polymerisation of the reaction intermediates. The kinetics of Maillard reaction was first-ordered reaction in the presence of phytic acid. Phytic acid was less effective than phosphate in the formation of acrylamide. When potato slices were treated with sodium phytate and calcium chloride successively, the formation of acrylamide was greatly suppressed.

  7. 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.

  8. Comprehensive investigation of the energetics of pyrimidine nucleoside formation in a model prebiotic reaction.

    PubMed

    Sheng, Yinghong; Bean, Heather D; Mamajanov, Irena; Hud, Nicholas V; Leszczynski, Jerzy

    2009-11-11

    The problem of beta-nucleoside formation under prebiotic conditions represents one of the most significant challenges to the "RNA world" hypothesis. The possibility exists that alternative bases may have come before the contemporary bases (i.e., A, G, C, and U), including bases that more readily form nucleosides. We previously reported the first successful synthesis of a pyrimidine nucleoside from a free base and a nonactivated sugar in a plausible prebiotic reaction. Here we present a detailed computational study on the reaction at the density functional theory (DFT) level. The catalytic role of a Mg(2+) ion on the reaction mechanism is also investigated. Our calculations demonstrate that a Mg(2+) ion, serving as a Lewis acid, can afford the necessary stabilization to the base and leaving water molecule during glycoside bond formation. The solvent effect is considered by the Onsager solvation model and also by an extended model with the addition of explicit water molecules within the SCRF solvation model. In addition, predictions regarding the formation of nucleosides from other pyrimidine bases are also addressed, providing valuable insights into what chemical features of the bases facilitate glycoside formation in drying-heating reactions.

  9. 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 ...

  10. 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 ...

  11. Field-theoretical description of the formation of a crack tip process zone

    NASA Astrophysics Data System (ADS)

    Boulbitch, Alexei; Korzhenevskii, Alexander L.

    2016-12-01

    The crack tip process zone is regarded as a region where the solid physical properties are altered due to high stress. They are controlled by the solid degrees of freedom existing within the zone and vanishing outside, and can be divided into two classes: (1) zones always existing at the tip and (2) those emerging as soon as certain conditions are met. We focus on the zones of the second kind and argue that they can be described analogously to phase transitions taking place locally. We report both a numerical and an analytical solution for the process zone. We find that the zone can only exist within a limited domain of the dynamic phase diagram, at one side of the phase transition line. We describe this domain and establish its dependence on the crack velocity. We show the existence of a critical crack velocity above which the zone cannot exist.

  12. 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

    2017-02-01

    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.

  13. 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.

  14. 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.

  15. Transition zone assembly and its contribution to axoneme formation in Drosophila male germ cells.

    PubMed

    Vieillard, Jennifer; Paschaki, Marie; Duteyrat, Jean-Luc; Augière, Céline; Cortier, Elisabeth; Lapart, Jean-André; Thomas, Joëlle; Durand, Bénédicte

    2016-09-26

    The ciliary transition zone (TZ) is a complex structure found at the cilia base. Defects in TZ assembly are associated with human ciliopathies. In most eukaryotes, three protein complexes (CEP290, NPHP, and MKS) cooperate to build the TZ. We show that in Drosophila melanogaster, mild TZ defects are observed in the absence of MKS components. In contrast, Cby and Azi1 cooperate to build the TZ by acting upstream of Cep290 and MKS components. Without Cby and Azi1, centrioles fail to form the TZ, precluding sensory cilia assembly, and no ciliary membrane cap associated with sperm ciliogenesis is made. This ciliary cap is critical to recruit the tubulin-depolymerizing kinesin Klp59D, required for regulation of axonemal growth. Our results show that Drosophila TZ assembly in sensory neurons and male germ cells involves cooperative actions of Cby and Dila. They further reveal that temporal control of membrane cap assembly by TZ components and microtubule elongation by kinesin-13 is required for axoneme formation in male germ cells.

  16. Modelling of cloud formation due to air-sea interactions in an energy-active zone

    NASA Astrophysics Data System (ADS)

    Kondratyev, K. Ya.; Khvorostyanov, V. I.

    1989-02-01

    A mesoscale 3D numerical model is described, with which detailed calculations have been made of turbulence and wind characteristics in the atmospheric boundary layer (ABL), as well as cloud particle size distribution, longwave and solar radiation fluxes and flux divergences, and atmosphere-ocean heat exchange. Based on numerical experiments simulating winter conditions of the Newfoundland energy-active zone of the ocean (EAZO), atmosphere-ocean energy exchange is investigated. It is shown that the basic mechanisms for the EAZO formation involve the following processes: (i) at the hydrological front between cold and warm ocean currents, the fluxes of sensible and latent heat grow significantly; (ii) at this front, in a particular synoptic situation, overcast low-level cloudiness forms, screening solar radiation so that in winter, the radiation budget at the front is reduced, and the radiative flux into the ocean is less than the energy release to the atmosphere; (iii) frequent occurrence of such synoptic situations with cloudiness decreases the oceanic enthalpy and creates negative SST anomalies. The transport of these anomalies by currents to the western coasts of the continents causes anomalies of weather and climate.

  17. 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.

  18. 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.

  19. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

    NASA Astrophysics Data System (ADS)

    George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

    2016-12-01

    The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

  20. Subduction-related rodingites from East Othris, Greece: Mineral reactions and physicochemical conditions of formation

    NASA Astrophysics Data System (ADS)

    Koutsovitis, Petros; Magganas, Andreas; Pomonis, Panagiotis; Ntaflos, Theodoros

    2013-07-01

    The partly to pervasively metasomatized doleritic and gabbroic dykes or small to medium sized bodies found in East Othris, within Mid to Late Jurassic serpentinized peridotites of ophiolitic units and ophiolitic mélange formations are classified as rodingites and can be divided into two types. Type 1 rodingites are mainly characterized by the frequent occurrence of prehnite, while Type 2 rodingites include mostly garnets and vesuvianite. Isocon analysis showed that rodingitization essentially occurred with mass and volume preservation. Desilification, depletion of alkalies, as well as Ca enrichment was more intense for the Type 2 rodingites. Al, Fe and Mg remained rather immobile, while Ti, Y, Zr and REE were variably depleted. Rodingitization took place in an intraoceanic subduction system. It occurred in three successive stages during the exhumation of the mafic-ultramafic mantle wedge rocks in a fore-arc setting within a serpentinitic subduction channel, which developed close to the slab. The incorporation of the mafic rocks to the subduction channel probably resulted after entraining a directed mantle flow towards the slab. The first stage of rodingitization formed mainly grossular, hydrogrossular, Ti- and Cr-bearing hydrogarnets and calcite under relatively acidic and mildly oxidizing physicochemical conditions, with increased CO2/H2O ratio. During the second and more extensive rodingitization stage, alkaline and reducing conditions prevailed and CO2/H2O ratio was decreased. The modeling of the mineral reactions of this stage, using the software winTWQ v. 2.34 in the CFMASH system, reveals that in Type 1 rocks prehnite replaced most of the initial garnet, while Type 2 rocks continued to be rodingitized, mostly forming grossular and/or hydrogrossular and chlorite. Hydrogrossular, instead of grossular, was crystallized from hydrous fluids under high silica activity. Type 2 rodingites underwent further rodingitization during the third stage, due to infiltration

  1. Silica-undersaturated reaction zones at a crust-mantle interface in the Highland Complex, Sri Lanka: Mass transfer and melt infiltration during high-temperature metasomatism

    NASA Astrophysics Data System (ADS)

    Fernando, G. W. A. R.; Dharmapriya, P. L.; Baumgartner, Lukas P.

    2017-07-01

    Sri Lanka is a crucial Gondwana fragment mostly composed of granulitic rocks in the Highland Complex surrounded by rocks with granulite to amphibolite grade in the Vijayan and Wanni Complex that were structurally juxtaposed during Pan-African orogeny. Fluids associated with granulite-facies metamorphism are thought to have controlled various lower crustal processes such as dehydration/hydration reactions, partial melting, and high-temperature metasomatism. Chemical disequilibrium in the hybrid contact zone between a near peak post-tectonic ultramafic enclave and siliceous granulitic gneiss at Rupaha within the Highland Complex produced metasomatic reaction zones under the presence of melt. Different reaction zones observed in the contact zone show the mineral assemblages phlogopite + spinel + sapphirine (zone A), spinel + sapphirine + corundum (zone B), corundum ( 30%) + biotite + plagioclase zone (zone C) and plagioclase + biotite + corundum ( 5%) zone (zone D). Chemical potential diagrams and mass balance reveal that the addition of Mg from ultramafic rocks and removal of Si from siliceous granulitic gneiss gave rise to residual enrichment of Al in the metasomatized mineral assemblages. We propose that contact metasomatism between the two units, promoted by melt influx, caused steady state diffusional transport across the profile. Corundum growth was promoted by the strong residual Al enrichment and Si depletion in reaction zone whereas sapphirine may have been formed under high Mg activity near the ultramafic rocks. Modelling also indicated that metasomatic alteration occurred at ca. 850 °C at 9 kbar, which is consistent with post-peak metamorphic conditions reached during the initial stage of exhumation in the lower crust and with temperature calculations based on conventional geothermometry.

  2. Determining the locus of a processing zone in an in situ oil shale retort through a well in the formation adjacent the retort

    SciTech Connect

    Ridley, R.D.

    1982-08-17

    The locus of a processing zone advancing through a fragmented permeable mass of formation particles in an in situ oil shale retort in a subterranean formation containing oil shale is determined by monitoring in a well extending through unfragmented formation adjacent the retort, for condition in the retort affected by the advancement of such a processing zone through the retort. Monitoring can be effected by placing means for monitoring such a condition in such a well extending through unfragmented formation adjacent the retort.

  3. 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.

  4. 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

  5. New Conceptual Model for Soil Treatment Units: Formation of Multiple Hydraulic Zones during Unsaturated Wastewater Infiltration.

    PubMed

    Geza, Mengistu; Lowe, Kathryn S; Huntzinger, Deborah N; McCray, John E

    2013-07-01

    Onsite wastewater treatment systems are commonly used in the United States to reclaim domestic wastewater. A distinct biomat forms at the infiltrative surface, causing resistance to flow and decreasing soil moisture below the biomat. To simulate these conditions, previous modeling studies have used a two-layer approach: a thin biomat layer (1-5 cm thick) and the native soil layer below the biomat. However, the effect of wastewater application extends below the biomat layer. We used numerical modeling supported by experimental data to justify a new conceptual model that includes an intermediate zone (IZ) below the biomat. The conceptual model was set up using Hydrus 2D and calibrated against soil moisture and water flux measurements. The estimated hydraulic conductivity value for the IZ was between biomat and the native soil. The IZ has important implications for wastewater treatment. When the IZ was not considered, a loading rate of 5 cm d resulted in an 8.5-cm ponding. With the IZ, the same loading rate resulted in a 9.5-cm ponding. Without the IZ, up to 3.1 cm d of wastewater could be applied without ponding; with the IZ, only up to 2.8 cm d could be applied without ponding. The IZ also plays a significant role in soil moisture distribution. Without the IZ, near-saturation conditions were observed only within the biomat, whereas near-saturation conditions extended below the biomat with the IZ. Accurate prediction of ponding is important to prevent surfacing of wastewater. The degree of water and air saturation influences pollutant treatment efficiency through residence time, volatility, and biochemical reactions.

  6. Formation of orthopyroxenite by reaction between peridotite and hydrous basaltic melt: an experimental study

    NASA Astrophysics Data System (ADS)

    Wang, Chunguang; Liang, Yan; Dygert, Nick; Xu, Wenliang

    2016-09-01

    The consequences of hydrous basaltic melts and peridotite interaction were examined experimentally in Au-Pd, Pt, and graphite capsules using the reaction couple method. Reactions between a hydrous basaltic andesite (4 wt% H2O) and dunite or lherzolite in an Au-Pd capsule at 1 GPa and 1200 °C produce a melt-bearing orthopyroxenite-dunite sequence. Reactions between a hydrous ferro-basalt and lherzolite in Pt or Au-Pd capsules at 0.8-2 GPa and 1250-1385 °C produce a melt-bearing orthopyroxenite-harzburgite sequence. Reactions between the ferro-basalt and lherzolite in graphite capsules (not designed to retain water) result in a melt-bearing dunite-harzburgite sequence at 1 GPa and a melt-bearing harzburgite-lherzolite sequence at 2 GPa. The orthopyroxenite from the hydrous reaction experiments has a high porosity, and it is separated by a sharp lithological interface from the dunite or harzburgite. Orthopyroxenes in the orthopyroxenite are large in size with resorbed olivine inclusions. Formation of the high-porosity orthopyroxenite in the hydrous melt-rock reaction experiments is determined by the liquidus phase relation of the interface reacting melt and reaction kinetics. Reaction between orthopyroxene-saturated hydrous melt and olivine at melt-rock interface produces orthopyroxenite. Water infiltration induces hydrous melting of the lherzolite, producing a dunite or an orthopyroxene-depleted harzburgite. Efficient diffusive exchange between the partial melt and the hydrous reacting melt promotes orthopyroxene-oversaturation around the melt-rock interfacial region. The simplified experiments reveal end-member processes for understanding the formation of orthopyroxenite in the upper mantle. The presence of orthopyroxenites in mantle samples is a strong indication of hydrous melt and peridotite interaction.

  7. Formation of {beta}-hydroxycarbonyls from the OH radical-initiated reactions of selected alkenes

    SciTech Connect

    Aschmann, S.M.; Arey, J.; Atkinson, R.

    2000-05-01

    {beta}-Hydroxycarbonyls can be formed from the gas-phase reactions of alkenes with the OH radical, both in the presence and in the absence of NO. To date, because of analytical difficulties, few data have been reported for the formation of this class of compound from the reactions of the OH radical with alkenes. The authors have determined that {beta}-hydroxy-ketones can be readily analyzed by gas chromatography, and in this work they have shown that in 1 atm of air the {beta}-hydroxyalkoxy radicals formed in the reactions of the OH radical with trans-2-butene, trans-3-hexene, 1-butene, and {alpha}-pinene in the presence of NO primarily decompose rather than react with O{sub 2}. Rate constant ratios k{sub d}/k{sub 0{sub 2}} (or lower limits thereof), where k{sub d} and k{sub 0{sub 2}} are respectively the rate constants for the decomposition and the reaction with 0{sub 2} of the intermediate {beta}-hydroxyalkoxy radicals, have been obtained for the reactions of the CH{sub 3}CH(O)CH-(OH)CH{sub 3}, CH{sub 3}CH{sub 2}CH(O)CH{sub 2}OH, and CH{sub 3}CH{sub 2}CH(O)CH(OH)CH{sub 2}-CH{sub 3} radicals at 296 {+-} 2 K and atmospheric pressure. Using the O{sub 3} reactions with the alkenes to generate OH radicals, the reactions of the OH radical to generate OH radicals, the reactions of the OH radical with trans-2-butene, trans-3-hexene, and {alpha}-pinene in the absence of NO lead to the formation of the expected {beta}-hydroxycarbonyls and (at least for trans-2-butene) the {alpha},{beta}-diol.

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

    DOE PAGES

    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

  9. Damage Zones and Microcrack Formation Associated with Laboratory Produced Extension Fractures

    NASA Astrophysics Data System (ADS)

    Bradley, E. E.; Boutt, D. F.; Goodwin, L. B.

    2011-12-01

    Both joint sets and fault-related fractures serve as important conduits for fluid flow. In the former case, they can strongly influence both permeability and permeability anisotropy, with implications for production of water, hydrocarbons and contaminant transport. The latter can affect issues of fluid flow, such as whether a given fault seals or leaks, as well as fault mechanics. These fractures are commonly interpreted as Natural Hydraulic Fractures (NHFs), i.e., fractures produced when pore fluid pressure exceeds the tensile strength of the rock. Various mathematical models have been a rich source of hypotheses to explain the formation and propagation of these fractures, but have provided only limited information about fracture spacing and nothing about processes of fracture initiation in originally intact rock. Recent laboratory experiments of French (2009) have advanced our understanding of mechanical controls on fracture initiation and spacing. Here, detailed analysis of both through-going fracture surfaces and microcrack distributions in experimentally deformed samples provide a deeper understanding of NHF processes and resulting geometric features in porous siliciclastic sedimentary rocks. We studied fractures in a homogeneous, isotropic, fine to medium-grained quartz arenite, a homogeneous, anisotropic, coarse-grained quartz-rich siltstone, and a heterogeneous, isotropic, medium-grained quartz arenite. Both homogeneous samples developed a single, through-going fracture surrounded by a halo, or damage zone, of microcracks during the experiment. The fracture in the homogenous isotropic sample formed in the center of the sample where the pore fluid pressure was highest. It is the most planar fracture in the three samples, and has a microcrack damage zone that is symmetrical and extends nearly 2 cm to either side of the fracture. The homogeneous anisotropic sample's fracture formed away from the location of maximum pore fluid pressure, and was apparently

  10. Fundamental Experiments Of Fluid-Rock Reaction Due To A Mechanochemical Process: Implication For Seismic Fault Zones

    NASA Astrophysics Data System (ADS)

    Saruwatari, K.; Kameda, J.; Tanaka, H.

    2003-12-01

    Fracture zones within active fault zones are known to be passages of fluids. The fluid penetration in the fracture zone leads into fluid-rock interaction that changes the physical and chemical properties of the fault zone materials, possibly affecting the dynamic behavior of the fault itself. The evidences of the interactions between fluids and destructed rocks are obtained as anomalous concentrations of gases and chemical elements along active faults (e.g., Wakita et al., 1980; Tanaka et al., 2001). One of the characteristic products is hydrogen gas that has been detected relative to fault activities since Wakita et al. (1980) found hydrogen anomalies along an active fault. The generation of hydrogen gas is due to the radical reaction between water molecule and active Si radicals on the new surface of crushed quartz grains (Kita et al., 1982; Kameda et al., in press). Another characteristic product in the fault zone is submicron size of low strength materials such as amorphous and clays which seem to be formed by fluid-mineral reactions like dissolution-precipitation and alteration reactions (e.g., Tanaka et al., 2001). In order to understand the fluid-rock reactions during the pulverization of rocks, we performed batch-style crushing experiments of single crystals of quartz, alkali feldspar and biotite and granites with pure water (pH7) under argon-filled conditions using a glove box at the ambient temperature and pressure. We measured pH of the solutions and hydrogen gas concentrations using a glass electrode and gas chromatograph, respectively. BET (Brunauer, Emmett and Teller) method was adopted for precise measurements of net surface areas of the samples, in order to estimate the destructed atomic bonds. Furthermore, cations and anions in the water are also measured by PerkinElmer atomic absorption spectrometry and Toso ion chromatograph. pH values decrease for the experiments of quartz single crystal with increasing crushing times, while the other single

  11. Boundary-reaction-diffusion model for oscillatory zoning in binary crystals grown from solution.

    PubMed

    Kalischewski, Felix; Lubashevsky, Ihor; Heuer, Andreas

    2007-02-01

    Oscillatory Zoning (OZ) is a phenomenon exhibited by many geologically formed crystals. It is characterized by quasiperiodic oscillations in the composition of a solid solution, caused by self-organization. We present a model for OZ. The growth mechanism applied includes species diffusion through the solution bulk, particle adsorption, surface diffusion, and subsequently desorption or incorporation into the crystal. This mechanism, in particular, can provide the synchronization effects necessary to reproduce the layered structure of experimentally obtained crystals, lacking in other models. We conduct a linear stability analysis combined with numerical simulations. Our results reproduce the experimental findings with respect to the patterns formed and a critical supersaturation necessary for OZ to occur.

  12. 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.

  13. Acrylamide formation from asparagine under low moisture Maillard reaction conditions. 2. Crystalline vs amorphous model systems.

    PubMed

    Robert, Fabien; Vuataz, Gilles; Pollien, Philippe; Saucy, Françoise; Alonso, Maria-Isabelle; Bauwens, Isabelle; Blank, Imre

    2005-06-01

    The formation of acrylamide was investigated in model systems based on asparagine and glucose under low moisture Maillard reaction conditions as a function of reaction temperature, time, physical state, water activity, and glass transition temperature. Equimolar amorphous glucose/asparagine systems with different water activities were prepared by freeze drying and were shown to quickly move to the rubbery state already at room temperature and a water activity of above 0.15. The acrylamide amounts were correlated with physical changes occurring during the reaction. Pyrolysis and kinetics of acrylamide release in amorphous and crystalline glucose/asparagine models indicated the importance of the physical state in acrylamide formation. In amorphous systems, acrylamide was generated in higher concentrations and at lower temperatures as compared to the crystalline samples. Time and temperature are covariant parameters in both systems affecting the acrylamide formation by thermal processes. On the other side, the water activity and glass transition temperature do not seem to be critical parameters for acrylamide formation in the systems studied.

  14. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space.

    PubMed

    Gamez-Garcia, Victoria G; Galano, Annia

    2017-10-05

    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  15. Impact of high-intensity ultrasound on the formation of lactulose and Maillard reaction glycoconjugates.

    PubMed

    Corzo-Martínez, Marta; Montilla, Antonia; Megías-Pérez, Roberto; Olano, Agustín; Moreno, F Javier; Villamiel, Mar

    2014-08-15

    The impact of high-intensity ultrasound (US) on the formation of lactulose during lactose isomerization and on the obtention of lysine-glucose glycoconjugates during Maillard reaction (MR) has been studied, respectively, in basic and neutral media. As compared to equivalent conventional heat treatments, a higher formation of furosine, as indicator of initial steps of MR, was observed together with more advance of the reaction in US treated samples, this effect being more pronounced with the increase of US amplitude (50-70%) and temperature (25-40 °C). Regarding the influence of US on lactulose formation, in general, in a buffered system (pH 10.0), US at 70% of amplitude and 60 °C increased the rate of lactose isomerization, higher values of lactulose, epilactose and galactose being observed in comparison to conventional heating. The results of this work showed an acceleration of both reactions by US, indicating its usefulness to promote the formation of functional ingredients. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Contrasting reactions of hydrated electron and formate radical with 2-thio analogues of cytosine and uracil.

    PubMed

    Prasanthkumar, Kavanal P; Alvarez-Idaboy, Juan R; Kumar, Pavitra V; Singh, Beena G; Priyadarsini, K Indira

    2016-10-19

    2-Thiocytosine (TC) and 2-thiouracil (TU) were subjected to hydrated electron (eaq(-)), formate radical (CO2˙(-)) and 2-hydroxypropan-2-yl radical ((CH3)2˙COH) reactions in aqueous medium. Transients were characterized by absorption spectroscopy and the experimental findings were rationalized by DFT calculations at LC-ωPBE and M06-2X levels using a 6-311+G(d,p) basis set and SMD solvation. In eaq(-) reactions, a ring N-atom protonated radical of TC and an exocyclic O-atom protonated radical of TU were observed via addition of eaq(-) and subsequent protonation by solvent molecules. However, two competing but simultaneous mechanisms are operative in CO2˙(-) reactions with TC and TU. The first one corresponds to formations of N(O)-atom protonated radicals (similar to eaq(-) reactions); the second mechanism led to 2 center-3 electron, sulfur-sulfur bonded neutral dimer radicals, TCdim˙ and TUdim˙. DFT calculations demonstrated that H-abstraction by CO2˙(-) from TC(TU) results in S-centered radical which upon combination with TC(TU) provide the dimer radical. In some cases, DFT energy profiles were further validated by CBS-QB3//M06-2X calculations. This is the first time report for a contradictory behavior in the mechanisms of eaq(-) and CO2˙(-) reactions with any pyrimidines or their thio analogues.

  17. Can Dietary Polyphenols Prevent the Formation of Toxic Compounds from Maillard Reaction?

    PubMed

    Del Turco, Serena; Basta, Giuseppina

    2016-01-01

    Polyphenols are functional compounds in edible vegetable and food such as tea, coffee and red wine and increasing evidence demonstrates a positive link between consumption of polyphenol-rich foods and disease prevention. In this review we have focused on the current knowledge of the potential anti-glycation effects of polyphenols, particularly in regard to their influence on Maillard reaction, a non-enzymatic reaction between amino acids and reducing sugars that contributes to the production of toxic compounds, mainly reactive carbonyl species, advanced glycation end-products (AGEs) and other toxicants. The Maillard reaction occurs in the human body during hyperglycemic condition, but it is well known as browning reaction in thermally processed foods and it is responsible for flavor and toxicant formation. Dietary polyphenols can have anti-glycation effects and actively participate in Maillard reaction, mitigating the AGE formation and the heat-induced production of toxic compounds. In a time in which the role of a healthy diet in the prevention of chronic diseases is welcome and the borderline between food and medicine is becoming very thin, an improved mechanistic knowledge of how polyphenols can function to reduce harmful and unhealthy substances is mandatory.

  18. 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.

  19. 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.

  20. Radionuclide reactions with groundwater and basalts from Columbia River basalt formations

    SciTech Connect

    Barney, G.S.

    1981-06-01

    Chemical reactions of radionuclides with geologic materials found in Columbia River basalt formations were studied. The objective was to determine the ability of these formations to retard radionuclide migration from a radioactive waste repository located in deep basalt. Reactions that can influence migration are precipitation, ion-exchange, complexation, and oxidation-reduction. These reactions were studied by measuring the effects of groundwater composition and redox potential (Eh) on radionuclide sorption on fresh basalt surfaces, a naturally altered basalt, and a sample of secondary minerals associated with a Columbia River basalt flow. In addition, radionuclide sorption isotherms were measured for these materials and reaction kinetics were determined. The radionuclides studied were /sup 137/Cs, /sup 85/Sr, /sup 75/Se, /sup 95m/Tc, /sup 237/Np, /sup 241/Am, /sup 226/Ra and /sup 237/Pu. The Freundlich equation accurately describes the isotherms when precipitation of radionuclides does not occur. In general, sorption increased in the order: basalt < altered basalt < secondary minerals. This increase in sorption corresponds to increasing surface area and cation exchange capacity. The Eh of the system had a large effect on technetium, plutonium, and neptunium sorption. Technetium(VII), Pu(VI), and Np(V) are reduced to Tc(IV), Pu(IV), and Np(IV), respectively, under Eh conditions expected in deep basalt formations. The kinetics of radionuclide sorption and basalt-groundwater reactions were observed over a period of 18 weeks. Most sorption reactions stabilized after about four weeks. Groundwater composition changed the least in contact with altered basalt. Contact with secondary minerals greatly increased Ca, K, and Mg concentrations in the groundwater.

  1. 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.

  2. Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void

    NASA Astrophysics Data System (ADS)

    Shan, Tzu-Ray; Thompson, Aidan P.

    2014-05-01

    We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N2 and H2O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

  3. Macroscopically structured polymer formation governed by spatial patterns in the Belousov Zhabotinsky reaction

    NASA Astrophysics Data System (ADS)

    Kalishyn, Yevhen Yu.; Khavrus, Vyacheslav O.; Strizhak, Peter E.; Seipel, Michael; Münster, Arno F.

    2002-09-01

    We report the formation of macroscopically structured cross-linked polyacrylamide hydrogel in the Belousov-Zhabotinsky (BZ) system (oxidation of malonic acid by bromate catalyzed by ferroin). Here, acrylamide, the cross-linker bis-acrylamide, and polymerization initiator are added into the BZ system. We show that the formation of waves and ripples in the polymer is governed by spatial structures emerging in the BZ system. Without any spatial structures in the BZ system only the formation of a spatially uniform polymer is observed. Without cross-linker, a spatially uniform polymer was observed as well. Structured polymer formation is caused by the interaction of chemical reactions in the BZ system and the polymerization process including gelation and cross-linking of the monomer units.

  4. Chiral glycine formation on cold interstellar grains by quantum tunneling hydrogen-deuterium substitution reactions

    NASA Astrophysics Data System (ADS)

    Oba, Yasuhiro; Watanabe, Naoki; Osamura, Yoshihiro; Kouchi, Akira

    2015-08-01

    We report experimental evidence that chiral glycine (NH2CHDCOOH) is formed by the surface reaction of normal glycine (NH2CH2COOH) solid with deuterium (D) atom at 12 K under the simulative conditions of interstellar molecular clouds. Chiral glycine formation is most likely initiated by the tunneling abstraction reaction of H atom by D atom followed by the addition of D atom to the glycine radical (NH2CHCOOH). Given that chiral glycine can form in such a primordial low-temperature environment, it might source molecular chirality as molecular clouds evolve into planetary systems.

  5. 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.

  6. 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.

  7. Formation of deeply bound kaonic atoms in (K-,N) reactions

    NASA Astrophysics Data System (ADS)

    Yamagata, J.; Nagahiro, H.; Kimura, R.; Hirenzaki, S.

    2007-10-01

    We study theoretically the (K-,N) reactions for the formation of the deeply bound kaonic atoms, which were predicted to be quasistable with narrow widths, using the Green's function method. We systematically consider various cases with different target nuclei and energies and find clear signals in the theoretical spectra for all cases considered in this article. The signals show very interesting structures, such as a RESONANCE DIP instead of a resonance peak. We discuss the origins of the interesting structures and the possibilities of obtaining new information on the existence of kaonic nuclei from the spectra of atomic state formations.

  8. 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.

  9. Formation of monazite via prograde metamorphic reactions among common silicates: implications for age determinations

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.; Malloy, Margaret A.

    2004-01-01

    Three lines of evidence from schists of the Great Smoky Mountains, NC, indicate that isogradic monazite growth occurred at the staurolite-in isograd at ˜600°C: (1) Monazite is virtually absent below the staurolite-in isograd, but is ubiquitous (several hundred grains per thin section) in staurolite- and kyanite-grade rocks. (2) Many monazite grains are spatially associated with biotite coronas around garnets, formed via the reaction Garnet + Chlorite + Muscovite = Biotite + Plagioclase + Staurolite + H 2O. (3) Garnets contain high-Y annuli that result from prograde dissolution of garnet via the staurolite-in reaction, followed by regrowth, and rare monazite inclusions occur immediately outside the annulus and in the matrix, but not in the garnet core. Larger monazite grains also exhibit quasi-continuous Th zoning with high Th cores and low Th rims, consistent with monazite growth via a single reaction and fractional crystallization during prograde growth. Common silicates may host sufficient P and LREEs that reactions among them can produce observable LREE phosphate. Specifically phosphorus contents of garnet and plagioclase are hundreds of parts per million, and dissolution of garnet and recrystallization of plagioclase could form thousands of phosphate grains several micrometers in diameter per thin section. LREEs may be more limiting, but sheet silicates and plagioclase can contain tens to ˜100 (?) ppm LREE, so recrystallization of these silicates to lower LREE contents could produce hundreds of grains of monazite per thin section. Monazite ages, determined via electron and ion microprobes, are ˜400 Ma, directly linking prograde Barrovian metamorphism of the Western Blue Ridge with the "Acadian" orogeny, in contrast to previous interpretations that metamorphism was "Taconian" (˜450 Ma). Interpretation of ages from metamorphic monazite grains will require prior chemical characterization and identification of relevant monazite-forming reactions, including

  10. 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.

  11. Formaldehyde Reactions with Amines and Ammonia: Particle Formation and Product Identification

    NASA Astrophysics Data System (ADS)

    Galloway, M. M.; Millage, K. D.; Rodriguez, A.; Sedehi, N.; Powelson, M. H.; De Haan, D. O.

    2012-12-01

    Aqueous phase reactions between carbonyls and amines or ammonium salts have recently been implicated in secondary organic aerosol and brown carbon formation processes. Formaldehyde is ubiquitous in the atmosphere, and is present in both the gas and aqueous phases. However, the reactions of formaldehyde in the aqueous phase have not been completely characterized. This study aims to determine the interactions between formaldehyde and amines or ammonium salts present in atmospheric droplets. Bulk phase reactions of formaldehyde with these reactive nitrogen-containing compounds were monitored with ESI-MS and NMR to determine reaction kinetics and for product characterization, while UV-Vis spectroscopy was used to monitor changes in light absorption over time. Hexamethylenetetramine was found to be a major product of the formaldehyde/ammonium sulfate reaction, appearing within minutes of mixing. No products were formed that absorbed light beyond 225 nm. Mono-disperse particles containing mixtures of formaldehyde and ammonium sulfate or an amine were dried and analyzed via SMPS to determine the non-volatile fraction of the reaction products. Similarly, aqueous droplets were dried in a humid atmosphere to determine residual aerosol sizes over time as a function of formaldehyde concentration. This work indicates that formaldehyde plays a key role in aqueous-phase organic processing, as it has been observed to contribute to both an increase and reduction in the diameter and volume of residual aerosol particles.

  12. Selective covalent bond formation in polypeptide ions via gas-phase ion/ion reaction chemistry.

    PubMed

    Han, Hongling; McLuckey, Scott A

    2009-09-16

    Primary amines present in protonated polypeptides can be covalently modified via gas-phase ion/ion reactions using bifunctional reagent ions. The use of reagent anions with a charge-bearing site that leads to strong interactions with the polypeptide, such as sulfonic acid, gives rise to the formation of a long-lived adduct. A distinct reactive functional group, an aldehyde in the present case, can then undergo reaction with the peptide. Collisional activation of the adduct ion formed from a reagent with an aldehyde group and a peptide ion with a primary amine gives rise to water loss in conjunction with imine (Schiff base) formation. The covalently bound modification is retained upon subsequent collisional activation. This work demonstrates the ability to selectively modify polypeptide ions in the gas phase within the context of a multistage mass spectrometry experiment.

  13. Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen

    2017-07-01

    Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of

  14. Radar studies of the distribution of the formation zones of the first radar echo of hail clouds

    NASA Astrophysics Data System (ADS)

    Inyukhin, V. S.; Kushchev, S. A.; Liev, K. B.; Makitov, V. S.

    2016-11-01

    The results of studying the regions of hail-cell formation in the North Caucasus are considered. The optimal range of the underlying surface heights for their generation is determined based on an analysis of 392 hail cells. It is shown that the majority of hail cells are formed in the zone where the heights of the underlying surface vary from 900 to 2400 m. The most favorable conditions for the formation of hail clouds are recorded in the northern slopes of the Skalistyi (Rocky) ridge. This region accumulates the main maxima of the frequency of first radar echo recording. The second group of the frequency maxima is located over the Pastbishchnyi (Pasturable) and the Lesistyi (Woody) ridges. The generalized scheme for the region under study is constructed of three zones of generation of the first radar echo of the hail cells. It is shown that approximately 70% of hail clouds are formed over submontane and mountainous regions in the central North Caucasus (zones 2 and 3). The directions of motion of hail cells are quantified for each identified zone.

  15. Polychronous formation of the ophiolite association in the Tekturmas zone of Central Kazakhstan inferred from geochronological and biostratigraphic data

    NASA Astrophysics Data System (ADS)

    Degtyarev, K. E.; Tolmacheva, T. Yu.; Tretyakov, A. A.; Kotov, A. B.; Yakubchuk, A. S.; Salnikova, E. B.; Wang, Kuo-Lun

    2017-01-01

    Plagiogranites and conodonts from chert intercalations in basalts of the ophiolite association in the Tekturmas zone of Central Kazakhstan were subjected to the U‒Pb geochronological and stratigraphic investigations, respectively. The age of plagiogranite crystallization is estimated to be 489 ± 8 Ma corresponding to the stratigraphic interval spanning from the uppermost Upper Cambrian to the lower Tremadocian. Conodonts from cherts of the Kuzek Formation are distributed along the section interval from the uppermost part of the Darriwilian (Middle Ordovician) to the lower part of the Sandbian (Upper Ordovician), which corresponds to the period of 457‒460 Ma. It is revealed that the formation of the ophiolite section in the Tekturmas zone was a multistage process lasting from the Late Cambrian to the initial Late Ordovician.

  16. 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.

  17. 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.

  18. 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.

  19. Self-organized nanostructured spherulitic crystal pattern formation in Belousov-Zhabotinsky type reaction system

    NASA Astrophysics Data System (ADS)

    Srivastava, Rohit; Srivastava, P. K.

    2013-11-01

    We report the formation of self-organized nanostructured spherulitic crystal pattern in a modified Belousov-Zhabotinsky (BZ) type system. In liquid phase, we observed the reaction system to exhibit well distinguishable spatial patterns including stripe and hexagonal structures. The solid phase nucleation was found to occur in the colloidal phase and nanostructured spherulitic crystal patterns were obtained as one of the final products. Transmission electron microscopy, scanning electron microscopy, optical microscopy, powder X-ray diffraction and Fourier transform infrared spectroscopy were used to characterize the spherulitic crystal pattern. The average diameter of the grown crystals was found to be ˜30-100 nm. In situ UV-Visible spectroscopic measurement exhibited damped oscillatory nature corresponding to ferroin in the reaction system. This oscillation was found to be well conjugated to the spherulitic structures. The paper elucidates the roles of the various possible factors behind such phase-transformation along with the plausible explanation of the corresponding reaction pathways.

  20. 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.

  1. 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.

  2. Negative collision energy dependence of Br formation in the OH + HBr reaction.

    PubMed

    Che, Dock-Chil; Matsuo, Takashi; Yano, Yuya; Bonnet, Laurent; Kasai, Toshio

    2008-03-14

    The reaction between HBr and OH leading to H(2)O and Br in its ground state is studied by means of a crossed molecular beam experiment for a collision energy varying from 0.05 to 0.26 eV, the initial OH being selected in the state |JOmega> = |3/2 3/2> by an electrostatic hexapole field. The reaction cross-section is found to decrease with increasing collision energy. This negative dependence suggests that there is no barrier on the potential energy surface for the formation pathway considered. The experimental results are compared with the previously reported quantum scattering calculations of Clary et al. (D. C. Clary, G. Nyman and R. Hernandez, J. Phys. Chem., 1994, 101, 3704), and briefly discussed in the light of skewed potential energy surfaces associated with heavy-light-heavy type reactions.

  3. Formation of the μ phase in the transition zone of a diffusion chromium aluminide coating on a nickel superalloy

    NASA Astrophysics Data System (ADS)

    Nemirovskii, Yu. R.; Khadyev, M. S.; Lesnikov, V. P.; Kuznetsov, V. P.; Galoyan, A. G.

    2008-10-01

    Transmission electron microscopy has shown the formation of two morphological types of the μ phase in the zone of a chromium aluminide coating on the ZhS36VI superalloy. Three types of orientation relationships between the crystal lattices of the μ and γ' phases have been revealed. The origin of the revealed morphological and crystallographic characteristics of the μ phase has been established.

  4. 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.

  5. 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

    2012-01-07

    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.

  6. 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.

  7. 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

  8. SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

    PubMed

    Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

    2006-05-01

    A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.

  9. Identification of hydrolysable tannins in the reaction zone of Eucalyptus nitens wood by high performance liquid chromatography--electrospray ionisation mass spectrometry.

    PubMed

    Barry, K M; Davies, N W; Mohammed, C L

    2001-01-01

    The first detailed analysis of the phenolic constituents of the reaction zones (tissue of antimicrobial defence) from the sapwood of a Eucalyptus spp. is presented. Plantation-grown Eucalyptus nitens trees with stem decay resulting from pruning wounds were sampled and extracts were prepared from healthy sapwood and from reaction zone tissue. Analysis by HPLC with ESI-MS revealed that a diverse range of hydrolysable tannins are present in both healthy sapwood and in reaction zone extracts, including over 30 gallotannins, ellagitannins and phenols. Eight tannins were unequivocally identified, including the gallotannins tri-O-galloyl-beta-D-glucose, tetra-O-galloyl-beta-D-glucose and penta-O-galloyl-beta-D-glucose, and the ellagitannins pedunculagin, tellimagrandin I, casuarinin, casuarictin and tellimagrandin II. The phenols gallic acid, ellagic acid and catechin were also identified. The ellagitannins (particularly pedunculagin) are considerably more abundant in the reaction zone than in the healthy sapwood and may contribute to the effectiveness of the reaction zone as an antimicrobial barrier.

  10. 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.

  11. High Resolution Surveys of the Water and Methanol Star Formation Masers in the Central Molecular Zone

    NASA Astrophysics Data System (ADS)

    Rickert, Matthew; Yusef-Zadeh, Farhad; Ott, Juergen; Meier, David S.; Krieger, Nico; SWAG

    2017-01-01

    We present some of the first high resolution fully interferometric surveys of 6.7 GHz methanol and 22 GHz water masers towards the Central Molecular Zone (CMZ). These masers are good signposts for early (<0.05 Myrs) star formation. Using the Jansky Very Large Array (VLA), we searched the inner 3 x 0.7 deg of the Galactic Center (GC) for methanol masers with resolutions of 0.9” (0.04 pc) and 0.4 km/s (8 kHz) and an average channel sensitivity of ~0.01 Jy/beam. With this high resolution and sensitivity, we have detected ~100 methanol masers, which is over a factor of two more than has previously been detected. We have also conducted two surveys of water masers in this region. As part of the Survey of Water and Ammonia in the Galactic Center (SWAG), the Australia Telescope Compact Array (ATCA) was used to survey a variety of molecular lines, including the 22 GHz water line. With the ATCA, we have detected over 200 water masers using resolutions of 26” (1 pc) and 2 km/s (60 kHz) and an average channel sensitivity of ~0.01 Jy/beam. Afterward, we conducted the first on-the-fly (OTF) VLA survey of water masers with improved resolutions of 0.7” (0.03 pc) and 0.4 km/s (26 kHz) and an average channel sensitivity of ~0.05 Jy/beam. Although the analysis of this OTF survey is not yet complete, we have already identified water masers that were not visible in the SWAG data.The improvement in the number of detected masers allows us to better analyze the distribution of these masers. We show that the SWAG water masers appear uniformly distributed along the Galactic plane, despite the asymmetry of the molecular gas distribution, where ~2/3 of the gas mass is located at positive Galactic longitudes. The methanol masers follow the molecular gas distribution, with a majority of the masers being found at positive longitudes. This could indicate a difference in the star forming history of these two parts of the CMZ and/or that the 22 GHz water masers are contaminated by water

  12. 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

  13. Effect of additives on mineral trioxide aggregate setting reaction product formation.

    PubMed

    Zapf, Angela M; Chedella, Sharath C V; Berzins, David W

    2015-01-01

    Mineral trioxide aggregate (MTA) sets via hydration of calcium silicates to yield calcium silicate hydrates and calcium hydroxide (Ca[OH]2). However, a drawback of MTA is its long setting time. Therefore, many additives have been suggested to reduce the setting time. The effect those additives have on setting reaction product formation has been ignored. The objective was to examine the effect additives have on MTA's setting time and setting reaction using differential scanning calorimetry (DSC). MTA powder was prepared with distilled water (control), phosphate buffered saline, 5% calcium chloride (CaCl2), 3% sodium hypochlorite (NaOCl), or lidocaine in a 3:1 mixture and placed in crucibles for DSC evaluation. The setting exothermic reactions were evaluated at 37°C for 8 hours to determine the setting time. Separate samples were stored and evaluated using dynamic DSC scans (37°C→640°C at10°C/min) at 1 day, 1 week, 1 month, and 3 months (n = 9/group/time). Dynamic DSC quantifies the reaction product formed from the amount of heat required to decompose it. Thermographic peaks were integrated to determine enthalpy, which was analyzed with analysis of variance/Tukey test (α = 0.05). Isothermal DSC identified 2 main exothermal peaks occurring at 44 ± 12 and 343 ± 57 minutes for the control. Only the CaCl2 additive was an accelerant, which was observed by a greater exothermic peak at 101 ± 11 minutes, indicating a decreased setting time. The dynamic DSC scans produced an endothermic peak around 450°C-550°C attributed to Ca(OH)2 decomposition. The use of a few additives (NaOCl and lidocaine) resulted in significantly less Ca(OH)2 product formation. DSC was used to discriminate calcium hydroxide formation in MTA mixed with various additives and showed NaOCl and lidocaine are detrimental to MTA reaction product formation, whereas CaCl2 accelerated the reaction. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  14. Neutrophil extracellular trap formation as innate immune reactions against the apicomplexan parasite Eimeria bovis.

    PubMed

    Behrendt, Jan Hillern; Ruiz, Antonio; Zahner, Horst; Taubert, Anja; Hermosilla, Carlos

    2010-01-15

    Eimeria bovis infections are under immunological control and recent studies have emphasized the role of early PMN-mediated innate immune responses in infected calves. Neutrophil extracellular traps (NETs) have recently been demonstrated to act as a killing mechanism of PMN against several pathogens. In the present study, the interactions of bovine PMN with sporozoites of E. bovis were investigated in this respect in vitro. For demonstration and quantification of NET formation, extracellular DNA was stained by Sytox Orange. Fluorescence images after Sytox Orange staining as well as scanning electron microscopy (SEM) showed NET formation to occur upon contact with E. bovis sporozoites. Exposure of PMN to viable sporozoites induced stronger NET formation than to dead or homogenized parasites. NET formation was abolished by treatment with DNase and could be reduced by diphenylene iodonium, which is described as a potent inhibitor of NADPH oxidase. After sporozoite and PMN co-culture, extracellular fibres were found attached to sporozoites and seemed to trap them, strongly suggesting that NETs immobilize E. bovis sporozoites and thereby prevent them from infecting host cells. Thus, transfer of sporozoites, previously being confronted with PMN, to adequate host cells resulted in clearly reduced infection rates when compared to PMN-free controls. NET formation by PMN may therefore represent an effector mechanism in early innate immune reactions against E. bovis. This is the first report indicating Eimeria-induced NET formation.

  15. Noncatalytic hydrogenation of naphthalene in nanosized membrane reactors with accumulated hydrogen and controlled adjustment of their reaction zone volumes

    NASA Astrophysics Data System (ADS)

    Soldatov, A. P.

    2017-05-01

    As part of ongoing studies aimed at designing the next generation of nanosized membrane reactors (NMRs) with accumulated hydrogen, the noncatalytic hydrogenation of naphthalene in pores of ceramic membranes (TRUMEM ultrafiltration membranes with D av = 50 and 90 nm) is performed for the first time, using hydrogen preadsorbed in a hybrid carbon nanostructure: mono- and multilayered oriented carbon nanotubes with graphene walls (OCNTGs) that form on inner pore surfaces. In this technique, the reaction proceeds in the temperature range of 330-390°C at contact times of 10-16 h. The feedstock is an 8% naphthalene solution in decane. The products are analyzed via chromatography on a quartz capillary column coated with polydimethylsiloxane (SE-30). It is established for the first time that in NMRs, the noncatalytic hydrogenation of naphthalene occurs at 370-390°C, forming 1,2,3,4-tetrahydronaphthalene in amounts of up to 0.61%. The rate constants and activation energy (123.5 kJ/mol) of the noncatalytic hydrogenation reaction are determined for the first time. The possibility of designing an NMR with an adjustable reaction zone volume is explored. Changes in the pore structure of the membranes after their modification with pyrocarbon nanosized crystallites (PNCs) are therefore studied as well. It is shown that lengthening the process time reduces pore size: within 23 h after the deposition of PNCs, the average pore radius ( r av) falls from 25 to 3.1 nm. The proposed approach would allow us to design nanoreactors of molecular size and conduct hydrogenation reactions within certain guidelines to synthesize new chemical compounds.

  16. 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

  17. 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

  18. Characterizing Pyroxene Reaction Space in Calcium-Aluminum Rich Inclusions: Oxidation During CAI Rim Formation

    NASA Astrophysics Data System (ADS)

    Dyl, K. A.; Young, E. D.

    2009-12-01

    We define the reaction space that controls changes in pyroxene composition in CAIs and Wark-Lovering (WL) rims in an oxidizing solar nebula. Ti-rich pyroxenes in CAIs record a sub-solar oxygen fugacity (Ti3+/Ti4+~1.5). WL rim pyroxenes in the CAI Leoville 144A have a distinctly lower oxidation state.This difference supports WL rim condensation in an environment of increasing O2(g) and Mg(g) (Simon et al. 2005). We used the following phase components to identify four linearly independent reactions (Thompson 1982): diopside, CaTs (Al2Mg-1Si-1), T3 (Ti3+AlMg-1Si-1), T4 (Ti4+Al2Mg-1Si-2), En (MgCa-1), perovskite, O(g), Mg(g), SiO(g), and Ca(g). Compositional variation in this system is dominated by two reactions. The first is oxidation of Ti3+ via reaction with O and Mg in the gas phase: 1.5 O(g) + Mg(g) → ¼ Di + [Ti4+Mg3/4Ti3+-1Ca-1/4Si-1/2] (1). Pyroxene is produced and En is introduced. The second reaction (2) is perovskite formation. It is observed in the WL rim of Leoville 144A, and experiments confirm that an elevated Ti component converts pyroxene to perovskite(Gupta et al. 1973). MgCa-1 is the third linearly independent reaction (3). They combine to give: ½ Di + x Ca(g)→ x Mg(g)+ Pv + [Mg1/2-xSiTi4+-1Ca-1/2+x](2,3). Unlike (1), pyroxene is consumed in this reaction. The parameter x defines the extent of Mg-Ca exchange. When x > 0.5, WL rim formation occurs in an environment where Mg is volatile and Ca condenses. The reaction space defined by reactions (1) and (2,3) describes the transition from CAI interior to WL rims. WL rim pyroxene Ti contents, [CaTs], and Ca < 1 pfu are all explained in this space. The fourth linearly independent reaction is SiO(g):1/8 Di + ¼ Mg(g)→ ¾ SiO(g) + [Mg3/8Ca1/8Ti4+Ti3+-1Si-1/2](4). Silica reduction forms Ti4+, releasing SiO(g). (4) does not describe the oxidation of Ti3+ in WL rim pyroxene, but (1) - (4) results in En formation directly from the gas phase. This may explain WL rim analyses that have Si contents in excess

  19. Grain boundary diffusion induced reaction layer formation in Fe/Pt thin films

    NASA Astrophysics Data System (ADS)

    Katona, G. L.; Vladymyrskyi, I. A.; Makogon, I. M.; Sidorenko, S. I.; Kristály, F.; Daróczi, L.; Csik, A.; Liebig, A.; Beddies, G.; Albrecht, M.; Beke, D. L.

    2014-04-01

    The solid-state reaction in Pt(15 nm)/Fe(15 nm) and Pt(15 nm)/Ag(10 nm)/Fe(15 nm) thin films after post-annealing at 593 K and 613 K for different annealing times has been studied. The structural properties of these samples were investigated by various methods including depth profiling with secondary neutral mass spectrometry, transmission electron microscopy, and X-ray diffraction. It is shown that after annealing at the above temperatures where the bulk diffusion processes are still frozen, homogeneous reaction layers of FePt and FePt with about 10 at.% Ag, respectively, have been formed. Corresponding depth profiles of the element concentrations revealed strong evidence that the formation mechanism is based on a grain boundary diffusion induced solid-state reaction in which the reaction interfaces sweep perpendicularly to the original grain boundary. Interestingly, X-ray diffraction indicated that in both thin-film systems after the solid-state reaction the ordered L10 FePt phase, which is the requested phase for future magnetic data storage applications, is also present.

  20. 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.

  1. 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

  2. Elucidation of reaction scheme describing malondialdehyde-acetaldehyde-protein adduct formation.

    PubMed

    Tuma, D J; Kearley, M L; Thiele, G M; Worrall, S; Haver, A; Klassen, L W; Sorrell, M F

    2001-07-01

    Malondialdehyde and acetaldehyde react together with proteins and form hybrid protein conjugates designated as MAA adducts, which have been detected in livers of ethanol-fed animals. Our previous studies have shown that MAA adducts are comprised of two distinct products. One adduct is composed of two molecules of malondialdehyde and one molecule of acetaldehyde and was identified as the 4-methyl-1,4-dihydropyridine-3,5-dicarbaldehyde derivative of an amino group (MDHDC adduct). The other adduct is a 1:1 adduct of malondialdehyde and acetaldehyde and was identified as the 2-formyl-3-(alkylamino)butanal derivative of an amino group (FAAB adduct). In this study, information on the mechanism of MAA adduct formation was obtained, focusing on whether the FAAB adduct serves as a precursor for the MDHDC adduct. Upon the basis of chemical analysis and NMR spectroscopy, two initial reaction steps appear to be a prerequisite for MDHDC formation. One step involves the reaction of one molecule of malondialdehyde and one of acetaldehyde with an amino group of a protein to form the FAAB product, while the other step involves the generation of a malondialdehyde-enamine. It appears that generation of the MDHDC adduct requires the FAAB moiety to be transferred to the nitrogen of the MDA-enamine. For efficient reaction of FAAB with the enamine to take place, additional experiments indicated that these two intermediates likely must be in positions on the protein of close proximity to each other. Further studies showed that the incubation of liver proteins from ethanol-fed rats with MDA resulted in a marked generation of MDHDC adducts, indicating the presence of a pool of FAAB adducts in the liver of ethanol-fed animals. Overall, these findings show that MDHDC-protein adduct formation occurs via the reaction of the FAAB moiety with a malondialdehyde-enamine, and further suggest that a similar mechanism may be operative in vivo in the liver during prolonged ethanol consumption.

  3. Electrochemical Formation of Fe(V) (O) and Mechanism of Its Reaction with Water During O-O Bond Formation.

    PubMed

    Pattanayak, Santanu; Chowdhury, Debarati Roy; Garai, Bikash; Singh, Kundan K; Paul, Amit; Dhar, Basab B; Gupta, Sayam Sen

    2017-03-08

    A detailed electrochemical investigation of a series of iron complexes (biuret-modified tetraamido iron macrocycles Fe(III) -bTAML), including the first electrochemical generation of Fe(V) (O), and demonstration of their efficacy as homogeneous catalysts for electrochemical water oxidation (WO) in aqueous medium are reported. Spectroelectrochemical and mass spectral studies indicated Fe(V) (O) as the active oxidant, formed due to two redox transitions, which were assigned as Fe(IV) (O)/Fe(III) (OH2 ) and Fe(V) (O)/Fe(IV) (O). The spectral properties of both of these high-valent iron oxo species perfectly match those of their chemically synthesised versions, which were thoroughly characterised by several spectroscopic techniques. The O-O bond-formation step occurs by nucleophilic attack of H2 O on Fe(V) (O). A kinetic isotope effect of 3.2 indicates an atom-proton transfer (APT) mechanism. The reaction of chemically synthesised Fe(V) (O) in CH3 CN and water was directly probed by electrochemistry and was found to be first-order in water. The pKa value of the buffer base plays a critical role in the rate-determining step by increasing the reaction rate several-fold. The electronic effect on redox potential, WO rates, and onset overpotential was studied by employing a series of iron complexes. The catalytic activity was enhanced by the presence of electron-withdrawing groups on the bTAML framework. Changing the substituents from OMe to NO2 resulted in an eightfold increase in reaction rate, while the overpotential increased threefold.

  4. Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

    NASA Astrophysics Data System (ADS)

    Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

    2016-12-01

    Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

  5. 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.

  6. Reactions of the OOH radical with guanine: Mechanisms of formation of 8-oxoguanine and other products

    NASA Astrophysics Data System (ADS)

    Kumar, Nagendra; Shukla, P. K.; Mishra, P. C.

    2010-09-01

    The mutagenic product 8-oxoguanine (8-oxoGua) is formed due to intermediacy of peroxyl (OOR) radicals in lipid peroxidation and protein oxidation-induced DNA damage. The mechanisms of these reactions are not yet understood properly. Therefore, in the present study, the mechanisms of formation of 8-oxoGua and other related products due to the reaction of the guanine base of DNA with the hydroperoxyl radical (OOH) were investigated theoretically employing the B3LYP and BHandHLYP hybrid functionals of density functional theory and the polarizable continuum model for solvation. It is found that the reaction of the OOH radical with guanine can occur following seven different mechanisms leading to the formation of various products including 8-oxoGua, its radicals, 5-hydroxy-8-oxoguanine and CO 2. The mechanism that yields 8-oxoGua as an intermediate and 5-hydroxy-8-oxoGua as the final product was found to be energetically most favorable.

  7. 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.

  8. 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.

  9. Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals.

    PubMed

    Elimelech, Orian; Liu, Jing; Plonka, Anna M; Frenkel, Anatoly I; Banin, Uri

    2017-08-21

    Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2 S) NCs through a redox reaction with iodine molecules (I2 ), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2 S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer

    NASA Astrophysics Data System (ADS)

    Ma, Yan; Diao, Yiwei; Zhang, Bingjie; Wang, Weiwei; Ren, Xinrong; Yang, Dongsen; Wang, Ming; Shi, Xiaowen; Zheng, Jun

    2016-12-01

    A proton transfer reaction ion-drift chemical ionization mass spectrometer (PTR-ID-CIMS) equipped with a hydronium (H3+O) ion source was developed and deployed near an industrial zone in the Yangtze River Delta (YRD) region of China in spring 2015 to investigate industry-related emissions of volatile organic compounds (VOCs). Air pollutants including formaldehyde (HCHO), aromatics, and other trace gases (O3 and CO) were simultaneously measured. Humidity effects on the sensitivity of the PTR-ID-CIMS for HCHO detection were investigated and quantified. The performances of the PTR-ID-CIMS were also validated by intercomparing with offline HCHO measurement technique using 2,4-dinitrophenylhydrazone (DNPH) cartridges and the results showed fairly good agreement (slope = 0.81, R2 = 0.80). The PTR-ID-CIMS detection limit of HCHO (10 s, three-duty-cycle averages) was determined to be 0.9-2.4 (RH = 1-81.5 %) parts per billion by volume (ppbv) based on 3 times the standard deviations of the background signals. During the field study, observed HCHO concentrations ranged between 1.8 and 12.8 ppbv with a campaign average of 4.1 ± 1.6 ppbv, which was comparable with previous HCHO observations in other similar locations of China. However, HCHO diurnal profiles showed few features of secondary formation. In addition, time series of both HCHO and aromatic VOCs indicated strong influence from local emissions. Using a multiple linear regression fit model, on average the observed HCHO can be attributed to secondary formation (13.8 %), background level (27.0 %), and industry-related emissions, i.e., combustion sources (43.2 %) and chemical productions (16.0 %). Moreover, within the plumes the industry-related emissions can account for up to 69.2 % of the observed HCHO. This work has provided direct evidence of strong primary emissions of HCHO from industry-related activities. These primary HCHO sources can potentially have a strong impact on local and regional air pollution formation

  11. Radiative capture reaction for 17Ne formation within a full three-body model

    NASA Astrophysics Data System (ADS)

    Casal, J.; Garrido, E.; de Diego, R.; Arias, J. M.; Rodríguez-Gallardo, M.

    2016-11-01

    Background: The breakout from the hot Carbon-Nitrogen-Oxigen (CNO) cycles can trigger the rp-process in type I x-ray bursts. In this environment, a competition between 15O(α ,γ )19Ne and the two-proton capture reaction 15O(2 p ,γ )17Ne is expected. Purpose: Determine the three-body radiative capture reaction rate for 17Ne formation including sequential and direct, resonant and nonresonant contributions on an equal footing. Method: Two different discretization methods have been applied to generate 17Ne states in a full three-body model: the analytical transformed harmonic oscillator method and the hyperspherical adiabatic expansion method. The binary p -15O interaction has been adjusted to reproduce the known spectrum of the unbound 16F nucleus. The dominant E 1 contributions to the 15O(2 p ,γ )17Ne reaction rate have been calculated from the inverse photodissociation process. Results: Three-body calculations provide a reliable description of 17Ne states. The agreement with the available experimental data on 17Ne is discussed. It is shown that the 15O(2 p ,γ )17Ne reaction rates computed within the two methods agree in a broad range of temperatures. The present calculations are compared with a previous theoretical estimation of the reaction rate. Conclusions: It is found that the full three-body model provides a reaction rate several orders of magnitude larger than the only previous estimation. The implications for the rp-process in type I x-ray bursts should be investigated.

  12. 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.

  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. Ozone process insights from field experiments - Part III: extent of reaction and ozone formation

    NASA Astrophysics Data System (ADS)

    Blanchard, Charles L.

    The analysis of ambient data offers a means of developing a qualitative understanding of the sensitivity of ozone formation at specific times and places to changes in VOC and NO x concentrations. The Integrated Empirical Rate (IER) model (Johnson, 1984, Proceedings of the Eighth International Clean Air Conference, Melbourne, Australia, pp. 715-731) and two revisions known as the Smog Production (SP) algorithm (Blanchard et al., 1999, Atmospheric Environment 33, 369-381; Chang et al., 1997, Atmospheric Environment 31, 2787-2794) are reviewed. Applied to ambient data, the algorithm requires measurements of ozone, NO, and either NO x or NO y and computes a quantity known as the extent of reaction. The extent of reaction is shown to be related to photochemical age and serves as an indicator of the sensitivity of instantaneous ozone production to changes in VOC or NO x concentrations. Extent of reaction alone is insufficient as an indicator of the sensitivity of ozone concentration to a complex upwind history of emission changes. Consideration of daily, hourly, and spatial patterns of extent of reaction is needed to interpret applications of the SP algorithm.

  15. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    PubMed

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

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

    PubMed

    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.

  17. Chemo-Marangoni convection driven by an interfacial reaction: pattern formation and kinetics.

    PubMed

    Eckert, K; Acker, M; Tadmouri, R; Pimienta, V

    2012-09-01

    A combined study devoted to chemo-Marangoni convection and the underlying kinetics is presented for a biphasic system in which surfactants are produced in situ by an interfacial reaction. The pattern formation studied in a Hele-Shaw cell in both microgravity and terrestrial environments initially shows an ensemble of chemo-Marangoni cells along a nearly planar interface. Soon, a crossover occurs to periodic large-scale interfacial deformations which coexist with the Marangoni cells. This crossover can be correlated with the autocatalytic nature of the interfacial reaction identified in the kinetic studies. The drastic increase in the product concentration is associated with an enhanced aggregate-assisted transfer after the critical micellar concentration is approached. In this context, it was possible to conclusively explain the changes in the periodicity of the interfacial deformations depending on the reactant concentration ratio.

  18. 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.

  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. Theoretical modeling of enzyme reactions: the thermodynamics of formation of compound 0 in horseradish peroxidase.

    PubMed

    Zazza, Costantino; Amadei, Andrea; Palma, Amedeo; Sanna, Nico; Tatoli, Simone; Aschi, Massimiliano

    2008-03-13

    In this paper, by using the perturbed matrix method (PMM) in combination with basic statistical mechanical relations both based on nanosecond time-scale molecular dynamics (MD) simulations, we quantitatively address the thermodynamics of compound 0 (Cpd 0) formation in horseradish peroxidase (HRP) enzyme. Our results, in the same trend of low-temperature experimental data, obtained in cryoenzymology studies indicate that such a reaction can be described essentially as a stepwise spontaneous process: a first step mechanically constrained, strongly exothermic proton transfer from the heme-H2O2 complex to the conserved His42, followed by a solvent-protein relaxation involving a large entropy increase. Critical evaluation of PMM/MD data also reveals the crucial role played by specific residues in the reaction pocket and, more in general, by the conformational fluctuations of the overall environment in physiological conditions.

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

    PubMed

    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.

  2. On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Schmidt, Johan A.; Kyte, Mildrid; Østerstrøm, Freja F.; Joelsson, Lars M. T.; Knap, Hasse C.; Jørgensen, Solvejg; Nielsen, Ole John; Murakami, Tatsuhiro; Johnson, Matthew S.

    2017-05-01

    The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52 ×10-16 cm3 s-1 at 10 Torr increasing to 7.20 ×10-16 cm3 s-1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3 ± 3.6) ×10-15 cm3 s-1 at 296 K and 700 Torr using relative-rate technique.

  3. A dynamic model for the formation of vesicular zones in ponded lava flows

    SciTech Connect

    Long, P.E.; McMillan, K.

    1988-12-01

    Thick (>30 m) flows of Columbia River basalt contain internal vesicular zones within otherwise dense, sparsely vesicular basalt. These zones are continuous over distances ranging from 2 to 30 km; most are characterized by abrupt transitions from vesicle-rich to vesicle-poor rock above and by gradational lower margins. The zones were formed by post-emplacement migration, coalescence, and entrapment of aqueous vapor bubbles. Under appropriate physicochemical conditions, bubbles nucleate at the lower solidification front and rise buoyantly until retarded by the higher viscosities preceding the upper solidifications front. Accumulation of bubbles against this ceiling occurs before freezing-in of the vesicles by the downward passage of the upper front. We have developed a one-dimensional dynamic model of the process of vesicular-zone emplacement by starting with the measured distribution of vesicles in a lava flow and calculating their movement according to Stokes' law as the flow is ''melted'' in the reverse of its solidification history. Estimates of the solidification history of the Cohassett flow were based on a previously developed cooling model. Simulated melting of the flow was accomplished by movement of the upper and lower solidification fronts in reverse time. 13 refs., 8 figs.

  4. Dynamic model of intermediate melting zones formation within the permeable lithosphere

    NASA Astrophysics Data System (ADS)

    Sorokin, Konstantin; Perepechko, Yury; Sharapov, Viktor; Chudnenko, Konstantin; Perepechko, Ludmila

    2017-04-01

    The paper discusses a model of mantle-crustal magmatic fluid systems in the collision domains in the southern and eastern margins of the Siberian Platform and as well within the mantle wedges beneath the epicontinental volcanic arcs of the Pacific Ocean. The study of the fluid-magmatic systems evolution is based on the nonstationary nonlinear dynamic model of heat and mass transfer of the multicomponent heterogeneous media, which takes into account the deformation of the rock. The interfacial interaction corresponding to the local parameters of the hydrodynamic flow is described within the model of flow-type multi-vessel reactor based on the minimization of the Gibbs potential. Numerical simulation of the wehrlitization of rocks of the deeper parts of the mantle wedge under the frontal area of the volcanic arcs of the Northwest Pacific Ocean demonstrates the following features of the hydrodynamic and metasomatic processes. A permeable region of the mantle wedge above the magmatic source quickly reaches a quasi-stationary distribution of pressure, which is somewhat less than lithostatic pressure in the rock massif. The variation of the interphase interaction parameters during fluid flow in a permeable zone and an increase in the interfacial viscous friction can lead to a significant change in the temperature distribution in the subsurface of the fluid system. At weak interfacial friction, the increase in temperature by a few degrees is recorded at the bottom flow. This leads to a significant change in the structure of a front metasomatic zoning that results in doubling of the carbonatization region developing in the zone of fluid penetration into the system. At that, the basification zone beyond the second area of carbonatization is more significant. A strong temperature increase appears due to a strong interfacial viscous friction, which leads to a qualitative change in the nature of the zoning evolution in the metasomatic columns which is observed along the fluid

  5. Assessment of the potential for ammonium nitrate formation and reaction in Tank 241-SY-101

    SciTech Connect

    Pederson, L.R.; Bryan, S.A.

    1994-08-01

    Two principal scenarios by which ammonium nitrate may be formed were considered: (a) precipitation of ammonium nitrate in the waste, and (b) ammonium nitrate formation via the gas phase reaction of ammonia and nitrogen dioxide. The first of these can be dismissed because ammonium ions, which are necessary for ammonium nitrate precipitation, can exist only in negligibly small concentrations in strongly alkaline solutions. Gas phase reactions between ammonia, nitrogen dioxide, and water vapor in the gas phase represent the most likely means by which ammonium nitrate aerosols could be formed in Tank 241-SY-101. Predicted ammonium nitrate formation rates are largely controlled by the concentration of nitrogen dioxide. This gas has not been detected among those gases vented from the wastes using Fourier Transform Infrared Spectrometry (FTIR) or mass spectrometry. While detection limits for nitrogen dioxide have not been established experimentally, the maximum concentration of nitrogen dioxide in the gas phase in Tank 241-SY-101 was estimated at 0.1 ppm based on calculations using the HITRAN data base and on FTIR spectra of gases vented from the wastes. At 50 C and with 100 ppm ammonia also present, less than one gram of ammonium nitrate per year is estimated to be formed in the tank. To date, ammonium nitrate has not been detected on HEPA filters in the ventilation system, so any quantity that has been formed in the tank must be quite small, in good agreement with rate calculations. The potential for runaway exothermic reactions involving ammonium nitrate in Tank 241-SY-101 is minimal. Dilution by non-reacting waste components, particularly water, would prevent hazardous exothermic reactions from occurring within the waste slurry, even if ammonium nitrate were present. 41 refs.

  6. The role of chemical processes and brittle deformation during shear zone formation and its potential geophysical implications

    NASA Astrophysics Data System (ADS)

    Goncalves, Philippe; Leydier, Thomas; Mahan, Kevin; Albaric, Julie; Trap, Pierre; Marquer, Didier

    2017-04-01

    Ductile shear zones in the middle and lower continental crust are the locus of interactions between mechanical and chemical processes. Chemical processes encompass metamorphic reactions, fluid-rock interactions, fluid flow and chemical mass-transfer. Studying these processes at the grain scale, and even the atom scale, on exposed inactive shear zones can give insights into large-scale geodynamics phenomena (e.g. crustal growth and mountain building through the reconstruction of P-T-t-D-Ɛ evolutionary paths. However, other major issues in earth sciences can be tackled through these studies as well. For instance, the mechanism of fluid flow and mass transfer in the deep crust where permeability should be small and transient is still largely debated. Studying exhumed inactive shear zones can also help to interpret several new geophysical observations like (1) the origin of tremor and very low frequency earthquakes observed in the ductile middle and lower crust, (2) mechanisms for generating slow slip events and (3) the physical origin of puzzling crustal anisotropy observed in major active crustal shear zones. In this contribution, we present a collection of data (deformation, petrology, geochemistry, microtexture) obtained on various shear zones from the Alps that were active within the viscous regime (T > 450°C). Our observations show that the development of a shear zone, from its nucleation to its growth and propagation, is not only governed by ductile deformation coeval with reactions but also involves brittle deformation. Although brittle deformation is a very short-lived phenomenon, our petrological and textural observations show that brittle failure is also associated with fluid flow, mass transfer, metasomatic reactions and recrystallization. We speculate that the fluids and the associated mineralogical changes involved during this brittle failure in the ductile crust might play a role in earthquake / tremor triggering below the brittle - ductile transition

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

    DOE PAGES

    Barron, S. C.; Knepper, R.; Walker, N.; ...

    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

  8. Kinetics and activation thermodynamics of methane monooxygenase compound Q formation and reaction with substrates.

    PubMed

    Brazeau, B J; Lipscomb, J D

    2000-11-07

    The transient kinetics of formation and decay of the reaction cycle intermediates of the Methylosinus trichosporium OB3b methane monooxygenase (MMO) catalytic cycle are studied as a function of temperature and substrate type and deuteration. Kinetic evidence is presented for the existence of three intermediates termed compounds O, P, and P forming after the addition of O(2) to diferrous MMO hydroxylase (H(r)) and before the formation of the reactive intermediate compound Q. The Arrhenius plots for these reactions are linear and independent of substrate concentration and type, showing that substrate does not participate directly in the oxygen activation phase of the catalytic cycle. Analysis of the transient kinetic data revealed only small changes relative to the weak optical spectrum of H(r) for any of these intermediates. In contrast, large changes in the 430 nm spectral region are associated with the formation of Q. The decay reaction of Q exhibits an apparent first-order concentration dependence for all substrates tested, and the observed rate constant depends on the substrate type. The kinetics of the decay reaction of Q yield a nonlinear Arrhenius plot when methane is the substrate, and the rates in both segments of the plot increase linearly with methane concentration. Together these observations suggest that at least two reactions with a methane concentration dependence, and perhaps two methane molecules, are involved in the decay process. When CD(4) is used as the substrate, a large isotope effect and a linear Arrhenius plot are observed. Analogous plots for all other MMO substrates tested (e.g., ethane) are linear, and no isotope effect for deuterated analogues is observed. This demonstrates that a step other than C-H bond breaking is rate limiting for alternative MMO substrates. A two step Q decay mechanism is proposed that provides an explanation for the lack of an isotope effect for alternative MMO substrates and the fact that rate of oxidation of

  9. In vitro surface reaction layer formation and dissolution of calcium phosphate cement-bioactive glass composites.

    PubMed

    Liu, Changsheng; Chen, Chien-Wen; Ducheyne, Paul

    2008-09-01

    Composites of hydrated calcium phosphate cement (CPC) and bioactive glass (BG) containing Si were immersed in vitro to study the effect of chemical composition on surface reaction layer formation and dissolution/precipitation behavior. The solutions used were 0.05 M tris hydroxymethyl aminomethane/HCl (tris buffer), tris buffer supplemented with plasma electrolyte (TE) with pH 7.4 at 37 degrees C, and this solution complemented with 10% newborn bovine serum (TES). The post-immersion solutions were analyzed for changes in Ca, PO(4) and Si concentrations. The reacted surfaces were analyzed using Fourier transform infrared (FTIR), and scanning electron microscopy with energy dispersive x-ray analysis. The sample weight variations after immersion were also determined. The results showed that the composition of the bioactive composite CPCs greatly affected their behavior in solution and the formation of apatite bioactive surface reaction layers. After immersion in the TE solution, Ca ions were taken up by all samples during the entire immersion duration. Initially, the P ion concentration increased sharply, and then decreased. This reaction pattern reveals the formation of an amorphous calcium phosphate layer on the surface of these composite CPCs. FTIR revealed that the layer was, in fact, poorly crystallized Ca-deficient carbonate apatite. The thickness of the layer was 12-14 microm and it was composed of rod-like apatite with directional arrangement. For immersion in the TES solution, the Ca and Si ion concentrations showed a similar behavior to that in TE, but the release rate of Si ions was higher. FTIR revealed that after TES immersion, not only did the typical, poorly crystallized, Ca-deficient carbonated apatite form, as it did in TE, but also the serum proteins co-adsorbed on the surface and thereby affected the surface reaction layer formation. A thinner apatite layer was formed and was composed of a micro-porous layer comprising rounded particles in a glue

  10. Overexpression of SlREV alters the development of the flower pedicel abscission zone and fruit formation in tomato.

    PubMed

    Hu, Guojian; Fan, Jing; Xian, Zhiqiang; Huang, Wei; Lin, Dongbo; Li, Zhengguo

    2014-12-01

    Versatile roles of REVOLUTA (REV), a Class III homeodomain-leucine zipper (HD-ZIP III) transcription factor, have been depicted mainly in Arabidopsis and Populus. In this study, we investigated the functions of its tomato homolog, namely SlREV. Overexpression of a microRNA166-resistant version of SlREV (35S::REV(Ris)) not only resulted in vegetative abnormalities such as curly leaves and fasciated stems, but also caused dramatic reproductive alterations including continuous production of flowers at the pedicel abscission zone (AZ) and ectopic fruit formation on receptacles. Microscopic analysis showed that meristem-like structures continuously emerged from the exodermises of the pedicel AZs and that ectopic carpels formed between the first and second whorl of floral buds in 35S::REV(Ris) plants. Transcriptional data suggest that SlREV may regulate genes related to meristem maintenance and cell differentiation in the development of the flower pedicel abscission zone, and modulate genes in homeodomain and MADS-box families and hormone pathways during fruit formation. Altogether, these results reveal novel roles of SlREV in tomato flower development and fruit formation.

  11. 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

  12. Global systematics of formation conditions of subduction zone magmas and their tectonic implications

    NASA Astrophysics Data System (ADS)

    Ogitsu, I.; Ozawa, K.

    2009-12-01

    Subduction zone magmatism plays an important role in material recycling of the earth’s interior, and it is imperative to understand melt generation mechanisms in the wedge mantle. The subduction zone is more complicated and diverse as a magma generation site than that of mid-ocean ridge or hot spot mostly because of the more significant and variable contribution of H2O-rich fluid expelled from the subducting slab, and because of the complexity of thermal and flow structures in the wedge mantle. The spatial variations of compositions of primary magmas in subduction zones have been recognized (e.g., Kuno, 1966; Sakuyama and Nesbitt, 1986), and are attributed to the diversity of melt segregation depth, degree of melting, or involvement of hydrous fluids with peculiar geochemical signature. It is particularly critical if melting at subduction zone is controlled mostly by the addition of H2O-rich fluid (Tatsumi, 1986; Iwamori, 1998) or by thermal and flow structure in the wedge mantle (Plank and Langmuir, 1993; Schmidt and Poli, 1998). In order to address this issue, quantitative estimation of melting conditions with clarification of the critical tectonic factors controlling magma generation is requisite and has been attempted in many studies with limited success. In this study, melting conditions of frontal volcanoes of world subduction zones are quantitatively estimated on the basis of major element composition of volcanic rocks. For quantitative estimation of melting conditions, we adopted appropriate models not only for mantle melting but also for fractional crystallization in the crust, simultaneous determination of both of which ensures the consistency of estimation procedure (Ogitsu and Ozawa, in prep.). Unknown parameters are optimized by least-squares method with input from a major element data of volcanic rocks. This approach is applicable to more differentiated rocks, which are not suitable for olivine addition methods widely used in estimation of primary

  13. 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

  14. Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2017-02-01

    Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

  15. 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...

  16. 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...

  17. 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.

  18. [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.

  19. Experimental study of the formation of high-resistivity zones at the gel/buffer interface in CE.

    PubMed

    Khozikov, Vyacheslav; Kosobokova, Olga; Citver, Gregory; Tyshko, George; Gavrilov, Dmitri N; Gudkov, George; Gorfinkel, Vera

    2007-02-01

    A novel, nondamaging method for experimental characterization of the formation and propagation of high-resistivity zones in CE, based on the measurement of time-dependent Joule heating on the outer capillary surface is proposed. The method detects propagation of resistive regions in capillaries in real time and allows the estimation of their velocity and resistance. The presented experimental data are in agreement with the results of the computer simulation as well as with previous data on the subject. The proposed method is useful for the development of new polymers as well as for the refinement and optimization of new CE protocols.

  20. Enthalpy of hydrogen bond formation in a protein-ligand binding reaction.

    PubMed Central

    Connelly, P R; Aldape, R A; Bruzzese, F J; Chambers, S P; Fitzgibbon, M J; Fleming, M A; Itoh, S; Livingston, D J; Navia, M A; Thomson, J A

    1994-01-01

    Parallel measurements of the thermodynamics (free-energy, enthalpy, entropy and heat-capacity changes) of ligand binding to FK506 binding protein (FKBP-12) in H2O and D2O have been performed in an effort to probe the energetic contributions of single protein-ligand hydrogen bonds formed in the binding reactions. Changing tyrosine-82 to phenylalanine in FKBP-12 abolishes protein-ligand hydrogen bond interactions in the FKBP-12 complexes with tacrolimus or rapamycin and leads to a large apparent enthalpic stabilization of binding in both H2O and D2O. High-resolution crystallographic analysis reveals that two water molecules bound to the tyrosine-82 hydroxyl group in unliganded FKBP-12 are displaced upon formation of the protein-ligand complexes. A thermodynamic analysis is presented that suggests that the removal of polar atoms from water contributes a highly unfavorable enthalpy change to the formation of C=O...HO hydrogen bonds as they occur in the processes of protein folding and ligand binding. Despite the less favorable enthalpy change, the entropic advantage of displacing two water molecules upon binding leads to a slightly more favorable free-energy change of binding in the reactions with wild-type FKBP-12. Images PMID:7510408

  1. Temperature perturbations evolution as a possible mechanism of exothermal reaction kernels formation in shock tubes

    NASA Astrophysics Data System (ADS)

    Drakon, A. V.; Kiverin, A. D.; Yakovenko, I. S.

    2016-11-01

    The basic question raised in the paper concerns the origins of exothermal reaction kernels and the mechanisms of detonation onset behind the reflected shock wave in shock-tube experiments. Using the conventional experimental technique, it is obtained that in the certain diapason of conditions behind the reflected shocks a so-called “mild ignition” arises which is characterized by the detonation formation from the kernel distant from the end-wall. The results of 2-D and 3-D simulations of the flow evolution behind the incident and reflected shocks allow formulation of the following scenario of ignition kernels formation. Initial stage during and after the diaphragm rupture is characterized by a set of non-steady gasdynamical processes. As a result, the flow behind the incident shock occurs to be saturated with temperature perturbations. Further evolution of these perturbations provides generating of the shear stresses in the flow accompanied with intensification of velocity and temperature perturbations. After reflection the shock wave interacts with the formed kernels of higher temperature and more pronounced kernels arise on the background of reactivity profile determined by moving reflected shock. Exothermal reaction starts inside such kernels and propagates into the ambient medium as a spontaneous ignition wave with minimum initial speed equal to the reflected shock wave speed.

  2. Enthalpy of hydrogen bond formation in a protein-ligand binding reaction.

    PubMed

    Connelly, P R; Aldape, R A; Bruzzese, F J; Chambers, S P; Fitzgibbon, M J; Fleming, M A; Itoh, S; Livingston, D J; Navia, M A; Thomson, J A

    1994-03-01

    Parallel measurements of the thermodynamics (free-energy, enthalpy, entropy and heat-capacity changes) of ligand binding to FK506 binding protein (FKBP-12) in H2O and D2O have been performed in an effort to probe the energetic contributions of single protein-ligand hydrogen bonds formed in the binding reactions. Changing tyrosine-82 to phenylalanine in FKBP-12 abolishes protein-ligand hydrogen bond interactions in the FKBP-12 complexes with tacrolimus or rapamycin and leads to a large apparent enthalpic stabilization of binding in both H2O and D2O. High-resolution crystallographic analysis reveals that two water molecules bound to the tyrosine-82 hydroxyl group in unliganded FKBP-12 are displaced upon formation of the protein-ligand complexes. A thermodynamic analysis is presented that suggests that the removal of polar atoms from water contributes a highly unfavorable enthalpy change to the formation of C=O...HO hydrogen bonds as they occur in the processes of protein folding and ligand binding. Despite the less favorable enthalpy change, the entropic advantage of displacing two water molecules upon binding leads to a slightly more favorable free-energy change of binding in the reactions with wild-type FKBP-12.

  3. 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.

  4. 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.

  5. Peptide Bond Formation through Gas-phase Reactions in the Interstellar Medium: Formamide and Acetamide as Prototypes

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-09-01

    A theoretical study of the reactions of NH_4+ with formaldehyde and CH_5+ 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.

  6. Organometallic nickel(III) complexes relevant to cross-coupling and carbon-heteroatom bond formation reactions.

    PubMed

    Zheng, Bo; Tang, Fengzhi; Luo, Jia; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2014-04-30

    Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. In addition to Ni(0) and Ni(II) intermediates, several Ni-catalyzed reactions are proposed to also involve odd-electron Ni(I) and Ni(III) oxidation states. We report herein the isolation, structural and spectroscopic characterization, and organometallic reactivity of Ni(III) complexes containing aryl and alkyl ligands. These Ni(III) species undergo transmetalation and/or reductive elimination reactions to form new C-C or C-heteroatom bonds and are also competent catalysts for Kumada and Negishi cross-coupling reactions. Overall, these results provide strong evidence for the direct involvement of organometallic Ni(III) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.

  7. AN EFFICIENT, NON-LINEAR STABILITY ANALYSIS FOR DETECTING PATTERN FORMATION IN REACTION DIFFUSION SYSTEMS

    PubMed Central

    HOLMES, WILLIAM R.

    2014-01-01

    Reaction diffusion systems are often used to study pattern formation in biological systems. However, most methods for understanding their behavior are challenging and can rarely be applied to complex systems common in biological applications. I present a relatively simple and efficient, non-linear stability technique that greatly aids such analysis when rates of diffusion are substantially different. This technique reduces a system of reaction diffusion equations to a system of ordinary differential equations tracking the evolution of a large amplitude, spatially localized perturbation of a homogeneous steady state. Stability properties of this system, determined using standard bifurcation techniques and software, describe both linear and non-linear patterning regimes of the reaction diffusion system. I describe the class of systems this method can be applied to and demonstrate its application. Analysis of Schnakenberg and substrate inhibition models is performed to demonstrate the methods capabilities in simplified settings and show that even these simple models have non-linear patterning regimes not previously detected. The real power of this technique however is its simplicity and applicability to larger complex systems where other non-linear methods become intractable. This is demonstrated through analysis of a chemotaxis regulatory network comprised of interacting proteins and phospholipids. In each case, predictions of this method are verified against results of numerical simulation, linear stability, asymptotic, and / or full PDE bifurcation analyses. PMID:24158538

  8. Reaction between drug substances and pharmaceutical excipients: formation of esters between cetirizine and polyols.

    PubMed

    Yu, He; Cornett, Claus; Larsen, Jesper; Hansen, Steen Honoré

    2010-11-02

    Reactions between active drug substances and excipients are of interest in the drug formulation process and should also be considered in the following storage of final preparations. Some excipients react more readily with certain chemical groups in drug substances and in the present paper the ester formation between a drug substance having a carboxylic acid moiety and some polyols are described. The drug substance cetirizine was chosen as the model substance as it is already marketed and used as a common drug for treatment of allergic reactions. Among the marketed products are oral solutions and oral drops containing excipients like sorbitol and glycerol. It was found that the carboxylic acid cetirizine readily reacts with sorbitol and glycerol to form monoesters. At a temperature as low as 40 degrees C, more than 1% of the cetirizine content was transformed into a monoester within 1 week using concentrations similar to those used in marketed preparations. The kinetic studies of the reaction performed at 40, 60 and 80 degrees C also revealed that the esters were unstable and they degraded especially at higher temperatures. Analysis of two marketed preparations having expiry dates in 2011 showed content of the cetirizine esters corresponding to a range from 0.1 to 0.3% of the declared cetirizine content.

  9. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate.

    PubMed

    Wu, Junjun; Khaled, Fethi; Ning, Hongbo; Ma, Liuhao; Farooq, Aamir; Ren, Wei

    2017-08-24

    We report a systematic chemical kinetics study of the H atom abstractions from ethyl formate (EF) by H, O((3)P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range 500-2500 K by the transition state theory (TST) in conjunction with the asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900-1321 K and 1.4-2.0 atm. Our theoretical rate constants of OH + EF → products agree well with the experimental results within 15% over the experimental temperature range of 900-1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  10. 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.

  11. Coke formation and carbon atom economy of methanol-to-olefins reaction.

    PubMed

    Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

    2012-05-01

    The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol.

  12. 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

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

    DOE PAGES

    Quan, Jiannong; Liu, Yangang; Liu, Quan; ...

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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 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 formation of secondary

  15. Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions.

    PubMed

    Nehr, Sascha; Bohn, Birger; Wahner, Andreas

    2012-06-21

    The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available.

  16. 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.

  17. Kinetics and mechanism for formation of enols in reaction of hydroxide radical with propene.

    PubMed

    Zhou, Chong-Wen; Li, Ze-Rong; Li, Xiang-Yuan

    2009-03-19

    Recently, enols have been found to be the common intermediates in hydrocarbon combustion flames (Taatjes et al. Science 2005, 308, 1887), but the knowledge of kinetic properties for such species in combustion flames is rare. Therefore in this work, particular attention is paid to the formation of enols in combustion flames. Starting with HO and propene (CH(3)CH=CH(2)), the reaction mechanism involving eight product channels has been investigated systematically. It is revealed that the electrophilic addition of OH to the double bond of CH(3)CH=CH(2) is unselective and the chemically activated adducts, CH(3)CHOH=CH(2) and CH(3)CH=CH(2)OH, may undergo dissociation in competition with H-abstractions. The kinetics and product branching ratios of the HO and propene reaction have been evaluated in the temperature range of 200-3000 K by Variflex code, based on the weak collision master equation/microcanonical variational RRKM theory. Available experimental kinetic data can be quantitatively reproduced by this study, with a minor adjustment (1.0 kcal/mol) of the OH central addition barrier. From the theoretical calculations with multiple reflection correction included, the total rate constant is fitted to k(t) = 6.07 x 10(-5)T(-2.54) exp(108/T) cm(3) x molecule(-1) x s(-1) in the range of 200-800 K and k(t) = 7.11 x 10(-23)T(3.38) exp(-1097/T) cm(3) x molecule(-1) x s(-1) in the range of 800-3000 K, which are in close agreement with experimental data. The branching ratios of enol channels are consistent with the observation in low-pressure flames and hence the reaction mechanisms presented here provide valuable descriptions of enol formations in hydrocarbon combustion chemistry.

  18. Turing pattern formation on the sphere for a morphochemical reaction-diffusion model for electrodeposition

    NASA Astrophysics Data System (ADS)

    Lacitignola, Deborah; Bozzini, Benedetto; Frittelli, Massimo; Sgura, Ivonne

    2017-07-01

    The present paper deals with the pattern formation properties of a specific morpho-electrochemical reaction-diffusion model on a sphere. The physico-chemical background to this study is the morphological control of material electrodeposited onto spherical particles. The particular experimental case of interest refers to the optimization of novel metal-air flow batteries and addresses the electrodeposition of zinc onto inert spherical supports. Morphological control in this step of the high-energy battery operation is crucial to the energetic efficiency of the recharge process and to the durability of the whole energy-storage device. To rationalise this technological challenge within a mathematical modeling perspective, we consider the reaction-diffusion system for metal electrodeposition introduced in [Bozzini et al., J. Solid State Electr.17, 467-479 (2013)] and extend its study to spherical domains. Conditions are derived for the occurrence of the Turing instability phenomenon and the steady patterns emerging at the onset of Turing instability are investigated. The reaction-diffusion system on spherical domains is solved numerically by means of the Lumped Surface Finite Element Method (LSFEM) in space combined with the IMEX Euler method in time. The effect on pattern formation of variations in the domain size is investigated both qualitatively, by means of systematic numerical simulations, and quantitatively by introducing suitable indicators that allow to assign each pattern to a given morphological class. An experimental validation of the obtained results is finally presented for the case of zinc electrodeposition from alkaline zincate solutions onto copper spheres.

  19. Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones.

    PubMed

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

    2013-10-21

    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 C=O 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 < CH3CHO < 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.

  20. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    NASA Astrophysics Data System (ADS)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  1. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

    PubMed

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U(VI)O2(2+)) coordinated by formate or acetate ligands. Anionic complexes containing U(VI)O2(2+) and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [U(VI)O2(O)(H)](-). Cationic species ultimately dissociate to make [U(VI)O2(OH)](+). Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to U(V)O2(+). Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [U(V)O2(O)](-). Loss of CH4 occurs by an intra-complex H(+) transfer process that leaves U(V)O2(+) coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [U(V)O2(O)](-). Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2. Graphical Abstract ᅟ.

  2. Visible-light induced isoindoles formation to trigger intermolecular Diels-Alder reactions in the presence of air.

    PubMed

    Lin, Chao; Zhen, Le; Cheng, Yong; Du, Hong-Jin; Zhao, Hui; Wen, Xiaoan; Kong, Ling-Yi; Xu, Qing-Long; Sun, Hongbin

    2015-06-05

    Visible-light induced isoindole formation triggered an intermolecular Diels-Alder reaction with dienophiles such as acetylenedicarboxylate and maleimides in the presence of air. The reaction resulted in excellent diastereoselctivity and high yields under mild reaction conditions. This protocol provides an atom-economical, transition-metal-free (TM-free) and straightforward approach to structurally diverse bridged-ring heterocycles from easily accessible molecules.

  3. Late Palaeozoic radiolarians from the Bentong-Raub suture zone, and the Semanggol formation of Peninsular Malaysia—initial results

    NASA Astrophysics Data System (ADS)

    Spiller, Frances C. P.; Metcalfe, Ian

    Cherts and tuffaceous siltstones from the Bentong-Raub suture zone, Peninsular Malaysia, have yielded radiolarians indicating Late Devonian (Famennian) and Early Carboniferous (Tournaisian, late? Tournaisian and Viséan) ages. Cerium anomalies from these Devonian and Carboniferous cherts indicate deposition in an open ocean. This ocean is interpreted to be the Palaeo-Tethys ocean which existed between Sibumasu and East Malaya during at least the Devonian and Early Carboniferous. Radiolarians extracted from siliceous sediments of the Semanggol Formation of NW Peninsular Malaysia have indicated both Early Permian and Late Permian (Guadalupian) ages. This extends the age of the Semanggol Formation down to the Early Permian and confirms the presence of a deep-marine basin in what is now NW Peninsular Malaysia during the Permian.

  4. Histidinyl radical formation in the self-peroxidation reaction of bovine copper-zinc superoxide dismutase.

    PubMed

    Gunther, Michael R; Peters, J Andrew; Sivaneri, Meena K

    2002-03-15

    In the absence of suitable oxidizable substrates, the peroxidase reaction of copper-zinc superoxide dismutase (SOD) oxidizes SOD itself, ultimately resulting in its inactivation. A SOD-centered free radical adduct of 2-methyl-2-nitrosopropane (MNP) was detected upon incubation of SOD with the spin trap and a hydroperoxide (either H(2)O(2) or peracetic acid). Proteolysis by Pronase converted the anisotropic electron paramagnetic resonance (EPR) spectrum of MNP/(center dot)SOD to a nearly isotropic spectrum with resolved hyperfine couplings to several atoms with non-zero nuclear spin. Authentic histidinyl radical (from histidine + HO(center dot)) formed a MNP adduct with a very similar EPR spectrum to that of the Pronase-treated MNP/(center dot)SOD, suggesting that the latter was centered on a histidine residue. An additional hyperfine coupling was detected when histidine specifically (13)C-labeled at C-2 of the imidazole ring was used, providing evidence for trapping at that atom. All of the experimental spectra were convincingly simulated assuming hyperfine couplings to 2 nearly equivalent nitrogen atoms and 2 different protons, also consistent with trapping at C-2 of the imidazole ring. Free histidinyl radical consumed oxygen, implying peroxyl radical formation. MNP-inhibitable oxygen consumption was also observed when cuprous SOD but not cupric SOD was added to a H(2)O(2) solution. Formation of 2-oxohistidine, the stable product of the SOD-hydroperoxide reaction, required oxygen and was inhibited by MNP. These results support formation of a transient SOD-peroxyl radical.

  5. Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.

    PubMed

    Verhamme, Ingrid M; Bock, Paul E

    2008-09-19

    Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.

  6. Evaluation of maillard reaction variables and their effect on heterocyclic amine formation in chemical model systems.

    PubMed

    Dennis, Cara; Karim, Faris; Smith, J Scott

    2015-02-01

    Heterocyclic amines (HCAs), highly mutagenic and potentially carcinogenic by-products, form during Maillard browning reactions, specifically in muscle-rich foods. Chemical model systems allow examination of in vitro formation of HCAs while eliminating complex matrices of meat. Limited research has evaluated the effects of Maillard reaction parameters on HCA formation. Therefore, 4 essential Maillard variables (precursors molar concentrations, water amount, sugar type, and sugar amounts) were evaluated to optimize a model system for the study of 4 HCAs: 2-amino-3-methylimidazo-[4,5-f]quinoline, 2-amino-3-methylimidazo[4,5-f]quinoxaline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,8-trimethyl-imidazo[4,5-f]quinoxaline. Model systems were dissolved in diethylene glycol, heated at 175 °C for 40 min, and separated using reversed-phase liquid chromatography. To define the model system, precursor amounts (threonine and creatinine) were adjusted in molar increments (0.2/0.2, 0.4/0.4, 0.6/0.6, and 0.8/0.8 mmol) and water amounts by percentage (0%, 5%, 10%, and 15%). Sugars (lactose, glucose, galactose, and fructose) were evaluated in several molar amounts proportional to threonine and creatinine (quarter, half, equi, and double). The precursor levels and amounts of sugar were significantly different (P < 0.05) in regards to total HCA formation, with 0.6/0.6/1.2 mmol producing higher levels. Water concentration and sugar type also had a significant effect (P < 0.05), with 5% water and lactose producing higher total HCA amounts. A model system containing threonine (0.6 mmol), creatinine (0.6 mmol), and glucose (1.2 mmol), with 15% water was determined to be the optimal model system with glucose and 15% water being a better representation of meat systems. © 2015 Institute of Food Technologists®

  7. Capillary zone electrophoresis-multiple reaction monitoring from 100 pg of RAW 264.7 cell lysate digest

    PubMed Central

    Sun, Liangliang; Li, Yihan; Champion, Matthew M.; Zhu, Guijie; Wojcik, Roza; Dovichi, Norman J.

    2013-01-01

    Capillary zone electrophoresis-multiple/single reaction monitoring (CZE-MRM/SRM), which employed an electrokinetically driven sheath-flow electrospray interface, was used for the rapid and highly sensitive detection of protein analytes in complex tryptic digests. MRM channels were developed against a commercial exponential mixture of bovine proteins. Five proteins spanning four orders of magnitude concentration range were confidently detected from only 2.5 ng of the digest mixture; the mass detection limits (S/N=3) of two detected proteins, alpha-casein and glutamate dehydrogenasewere about 600 zmole and 30 amole, respectively. This technique was then applied to a RAW 264.7 cell lysate digest. Three proteins were confidently and reproducibly detected from 100 pg of this digest. The sample amount corresponds to the approximate protein content from a single cell, which suggests that CZE-MRM may be a useful analytical tool in chemical cytometry. In addition to providing highly sensitive detection of proteins in complex mixtures, this system is highly rapid; migration time of the protein digests was less than 10 min. PMID:23591184

  8. Contribution of the photo-Fenton reaction to hydroxyl radical formation rates in river and rain water samples.

    PubMed

    Nakatani, Nobutake; Ueda, Marina; Shindo, Hirotaka; Takeda, Kazuhiko; Sakugawa, Hiroshi

    2007-09-01

    The hydroxyl radical (OH radical) formation rates from the photo-Fenton reaction in river and rain water samples were determined by using deferoxamine mesylate (DFOM), which makes a stable and strong complex with Fe(III), resulting in a suppression of the photo-Fenton reaction. The difference between the OH radical formation rates with and without added DFOM denotes the rate from the photo-Fenton reaction. The photoformation rates from the photo-Fenton reaction were in the range of 0.7 - 45.8 x 10(-12) and 2.7 - 32.3 x 10(-12) M s(-1) in river and rain water samples, respectively. A strong positive correlation between the OH radical formation rate from the photo-Fenton reaction and the amount of fluorescent matter in river water suggests that fluorescent matter, such as humic substances, plays an important role in the photo-Fenton reaction. In rain water, direct photolysis of hydrogen peroxide was an important source of OH radicals as well as the photo-Fenton reaction. The contributions of the photo-Fenton reaction to the OH radical photoformation rates in river and rain water samples were in the ranges of 2 - 29 and 5 - 38%, respectively. Taking into account the photo-Fenton reaction, 33 - 110 (mean: 80) and 42 - 110 (mean: 84)% of OH radical sources in river and rain water samples, respectively, collected in Hiroshima prefecture were elucidated.

  9. Multiple competing pathways for chemical reaction: drastic reaction shortcut for the self-catalytic double-helix formation of helicene oligomers.

    PubMed

    Kushida, Yo; Saito, Nozomi; Shigeno, Masanori; Yamaguchi, Masahiko

    2017-02-01

    Competition among multiple pathways in a chemical reaction exhibits notable kinetic phenomena, particularly when amplification by self-catalysis is involved. A pseudoenantiomeric 1 : 1 mixture of an aminomethylene helicene (P)-tetramer and an (M)-pentamer formed enantiomeric hetero-double helices B and C in solution when random coil A was cooled. When a solution of A at 70 °C was directly cooled to 25 °C, the A-to-B reaction was predominant, then B was slowly converted to C over 60 h. The slow conversion in the A-to-B-to-C reaction was due to the formation of the hetero-double helix B, which was an off-pathway intermediate, and the slow B-to-C conversion. In contrast, when a solution of A at 70 °C was snap-cooled to -25 °C before then maintaining the solution at 25 °C, the A-to-C reaction predominated, and the formation of C was complete within 4 h. The reactions involve competition between the self-catalytic A-to-B and A-to-C pathways, where B and C catalyze the A-to-B and A-to-C reactions, respectively. Subtle differences in the initial states generated by thermal pretreatment were amplified by the self-catalytic process, which resulted in a drastic reaction shortcut.

  10. HSO2+ formation from ion-molecule reactions of SO2.+ with water and methane: two fast reactions with reverse temperature-dependent kinetic trend.

    PubMed

    Cartoni, Antonella; Catone, Daniele; Bolognesi, Paola; Satta, Mauro; Markus, Pal; Avaldi, Lorenzo

    2017-02-08

    In this work an experimental and theoretical study on the formation of HSO2+ ion from the SO2.+ + CH4 and SO2.+ + H2O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation has been used to produce the SO2.+ ion in excited ro-vibrational levels of the ionic ground state X2A1 and mass spectrometry has been employed to identify the product ions. Calculations in the frame of the density functional theory and variational transtition state theory have been combined to explore the dynamics of the reactions. The experimental results show that HSO2+ is the only product in both reactions. Its yield decreases monotonically with photon energy in the SO2.+ + H2O reaction, while it decreases at first and then increases in the SO2.+ + CH4 reaction. Theory confirms this trend by calculating the rate constants at different temperatures and explains the results by means of the polar, spin and charge effects as well as structural reorganization occuring in the reaction coordinate. The dynamic behavior observed in these two reactions is of general and fundamental interest. It can also provide some insights in the role of these reactions in astrochemistry as well as in their use as models for bond-activation reactions.

  11. 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

  12. 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.

  13. 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.

  14. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. 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 catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  15. 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.

  16. Kinetics of Mn3+-oxalate formation and decay in reactions catalyzed by manganese peroxidase of Ceriporiopsis subvermispora

    Treesearch

    Ulises. Urzua; Philip J. Kersten; Rafael. Vicuna

    1998-01-01

    The kinetics of Mn3+- oxalate formation and decay were investigated in reactions catalyzed by manganese peroxidase (MnP) from the basiomycete Ceriporiopsis subvermispora in the absence of externally added hydrogen peroxide. A characteristic lag observed in the formation of this complex was shortened by glyoxylate or catalytic amounts of Mn3+ or hydrogen peroxide. MnP...

  17. 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.

  18. 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.

  19. Coke formation on HFAU and HEMT zeolites. Influence of the reaction temperature and propene pressure

    NASA Astrophysics Data System (ADS)

    Doka Nassionou, G. A.; Magnoux, P.; Guisnet, M.

    1999-02-01

    The formation of coke from propene (Pp = 1.3 kPa and 13 kPa) was investigated on HFAU and HEMT zeolites in a microbalance for temperatures ranging from 120 °C to 450 °C. For both zeolites, the greater the propene pressure and the lower the temperature the faster the initial coke formation. However for high propene pressure, initial coke formation is faster with HEMT zeolite. This can be related to the stronger acidity of the HEMT sample. For low propene pressure and after 420 minutes of coking, a minimum in coke is observed for T = 350 ^circC, which can be related to the difference between the rate of formation and the rate of retention of coke molecules. At low temperature, due to their low volatility, oligomers are easily formed and retained in the zeolite pores. These molecules can be totally eliminated by an adequate thermal treatment in vacuum. At higher temperature, only aromatic or polyaromatic compounds which present a size larger than the pore apertures can be retained in the cavities of the zeolites. The greater the reaction time, the faster the retention. Whatever the reaction temperature, coke molecules are more homogeneously distributed in the HEMT crystallites than in those of HFAU samples. For this latter zeolite coke molecules are preferentially formed in the cavities located near the outer surface of the crystallites (shell coking). La formation de coke à partir du propène (Pp = 1,3 et 13 kPa) a été étudiée en microbalance sur zéolithes HFAU et HEMT dans une gamme de température variant de 120 à 450°C. La vitesse initiale de formation de coke dépend de la pression du propène, de la température et également de la zéolithe. Ainsi, pour une forte pression en propène, la vitesse initiale de formation de coke est toujours plus importante sur HEMT que sur HFAU. Ceci est à relier à la plus grande acidité et à la présence de sites acides plus forts sur HEMT. Après 420 minutes de réaction, et pour une faible pression en propène le

  20. Trichloramine reactions with nitrogenous and carbonaceous compounds: kinetics, products and chloroform formation.

    PubMed

    Soltermann, Fabian; Canonica, Silvio; von Gunten, Urs

    2015-03-15

    Trichloramine is a hazardous disinfection by-product that is of particular relevance in indoor swimming pools. To better understand its fate in pool waters, apparent second order rate constants (kapp) at pH 7 for its reaction with several model compounds were determined. kapp values at pH 7 for nitrogenous compounds were found to increase in the following order: ammonia ∼ amides (∼10(-2)-10(-1) M(-1) s(-1)) < primary amines (∼10(-1)-10(0) M(-1) s(-1)) < relevant body fluid compounds (l-histidine, creatinine) (∼10(0)-10(1) M(-1) s(-1)) < secondary amines (∼10(1)-10(2) M(-1) s(-1)) < trimethylamine (∼10(3) M(-1) s(-1)). kapp values at pH 7 of trichloramine with hydroxylated aromatic compounds (∼10(2)-10(5) M(-1) s(-1)) are higher than for the nitrogenous compounds and depend on the number and position of the hydroxyl groups (phenol < hydroquinone < catechol < resorcinol). The measurement of kapp as a function of pH revealed that mainly the deprotonated species react with trichloramine. The reaction of trichloramine with Suwannee River and Pony Lake fulvic acid standards showed a decrease of their reactivity upon chlorination, which can be related to the electron donating capacity and the SUVA254. Chlorinated nitrogenous compounds (e.g. uric acid) also have a reduced reactivity with trichloramine. Hence, the residual chlorine in pool water hinders a fast consumption of trichloramine. This explains why trichloramine degradation in pool water is lower than expected from the reactivity with the estimated bather input. Trichloramine also has the potential to form secondary disinfection by-products such as chlorinated aromatic compounds or chloroform by electron transfer or Cl(+)-transfer reactions. The chloroform formation from the reaction of trichloramine with resorcinol occurs with a similar yield and rate as for chlorination of resorcinol. Since the trichloramine concentration in pool water is commonly about one order of

  1. Oligomerization reactions for precursors to secondary organic aerosol: Comparison between two formation mechanisms for the oligomeric hydroxyalkyl hydroperoxides

    NASA Astrophysics Data System (ADS)

    Zhao, Qiangli; Wang, Weina; Liu, Fengyi; Lü, Jian; Wang, Wenliang

    2017-10-01

    To better understand the formation mechanism of oligomeric hydroxyalkyl hydroperoxides HOROO(SCI)nH composed of stabilized Criegee intermediate (SCI) as a chain unit, the reactions of SCI with hydroxyalkyl hydroperoxides (HOROOH) and hydroxyalkylperoxy radical (HORO2) as well as HO2 radical were investigated. For the reactions of HORO2 + SCI, two preferred pathways involving a SCI insertion in HOROOH hydroperoxide bond can be found, and the formation of HOROO(SCI)H is the dominant pathway in the reaction of HOCH2(CH3)2COOH + (CH3)2COO. The structures of the HORO2, HOROOH as well as the SCIs play a crucial role in determining the reactivity of the oligomerization. Both the reactions of HORO2 + SCI + HO2 and HOROOH + SCI could be the source of the processors to the formation of secondary organic aerosol (SOA). But from the point of free energy barriers, the formation of HOROO(SCI)H prefers to follow the mechanism involving initiation by the reaction of a HORO2 and a SCI, sequential addition of SCIs, and termination by reaction with the HO2 radical. The rate coefficients show negative temperature dependence and vary in different systems depending on the reactants. The reaction process and constituents of the products can be regulated by temperature and reactants.

  2. 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

  3. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: putative formation of a copper(I)-peroxynitrite intermediate.

    PubMed

    Kalita, Apurba; Kumar, Pankaj; Mondal, Biplab

    2012-05-14

    The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.

  4. 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

  5. Wave Accumulation and the Formation of the South Atlantic Convergence Zone

    NASA Astrophysics Data System (ADS)

    Hirata, F. E.; Webster, P. J.; Hoyos, C.; Kim, H.

    2011-12-01

    Convectively active phases of the South Atlantic Convergence Zone (SACZ) are associated with extreme episodes of rainfall over a large and densely inhabited area of Eastern South America. The SACZ is usually defined as a northwest-southeast oriented band of cloudiness extending from the Amazon basin into the South Atlantic Ocean with a varying spectral structure along its axis. Close to the equator, intraseasonal and synoptic variations are less energetic. To the southeast, intraseasonal variability peaks over the Brazilian coast south of 12oS and synoptic disturbances gain importance in the subtropics over the ocean. The spectral structure and orientation of the SACZ strongly resembles features observed in the South Pacific Convergence Zone (SPCZ). Widlansky et al. (2010) showed that the group speed of synoptic Rossby waves is reduced in a region of negative zonal stretching deformation in the vicinity of the SPCZ, causing wave energy density to accumulate. They also demonstrate that the zonal SST gradient determines the location of the negative zonal stretching deformation region and, consequently, the orientation of the convergence zone. On the other hand, a recent paper by Ferreira et al. (2011) proposed that the onset of the first SACZ of the season is triggered after a change in behavior of propagating troughs forced by the development of the Bolivian High. This upper-level high has its origins associated with Amazon convection and enhances anticyclonic shear in the northern flank of the subtropical jet. The horizontal shear causes the transient extratropical disturbances to thin and tilt westward. Here we present evidences that the increasing strength of the upper-level high during late spring contributes to the increase of horizontal anticyclonic shear in the northern flank of the subtropical jet and to a more negative zonal stretching deformation in the subtropical SACZ domain. Both factors may act in concert to alter the shape and propagation of synoptic

  6. The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

    NASA Astrophysics Data System (ADS)

    Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.

    2013-12-01

    The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

  7. 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

  8. Time-dependent insulin oligomer reaction pathway prior to fibril formation: cooling and seeding.

    PubMed

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

    2009-10-01

    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 are 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 degrees 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 beta-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 degrees C) but are also continuously formed during cooling at pH 1.6 and 25 degrees C. Within the time-scale of the experiments, only after increasing the temperature to 65 degrees 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 degrees C) result in a decrease in the mean length of the fibers when placed at 65 degrees C. Fits of an empirical model to the data provide quantitative measures of the delay in the lag-time during the nucleation process and

  9. Hydroxy-group effect on the regioselectivity in a photochemical oxetane formation reaction (the Paternò-Büchi Reaction) of geraniol derivatives.

    PubMed

    Hisamoto, Ken; Hiraga, Yoshikazu; Abe, Manabu

    2011-09-01

    The Paternò-Büchi (PB) reaction of geraniol derivatives 1, which contain allylic alcohol functionality and unfunctionalized double bonds, with benzophenone was investigated to see the effect of the hydroxyl group on the regioselectivity of the oxetane formation, i.e., 2/3. At low concentration of geraniol (1a), oxetanes 2a and 3a were formed in a ratio of 2a/3a = ca. 50/50. The oxetane 2a is derived from the PB reaction at the allylic alcohol moiety, whereas the PB reaction at the unfunctionalized double bond produces the oxetane 3a. The PB reaction of the hydroxy-protected methyl ether 1b and acetate 1c gave selectively oxetanes 3b,c derived from the reaction at the more nucleophilic double bond, 2/3∼ 15/85. The hydroxyl-group effect was found to be small, but apparently increased the formation of 2a in the PB reaction with geraniol (1a).

  10. 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.

  11. Isomer-specific product formation in the proton transfer reaction of HOCO+ with CO

    NASA Astrophysics Data System (ADS)

    Carrascosa, Eduardo; Stei, Martin; Kainz, Martin A.; Wester, Roland

    2015-12-01

    The proton transfer reaction HOCO++CO → HCO+/HOC+ has been studied using crossed-beam velocity map imaging. Angular and energy differential cross sections were obtained for collision energies from 0.3 to 2.3 eV. Scattering in forward direction together with a prominent scattering angle-dependent internal excitation is found at all collision energies. The exothermic HCO+ product appears to be very dominant even at energies above the energy threshold for the formation of metastable HOC+ ion. To determine the HOC+ contribution for different angular ranges, a model has been developed. We obtain an upper limit for the HOC+ product isomer fraction of <2%. In theoretical calculations, we find the CO2-catalysed isomerisation channel to be energetically accessible. However, it may not have a strong impact on the isomer ratio. Chemical dynamics simulations are needed to shed more light on this question.

  12. 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.

  13. [Formation and reactions of biogenic manganese oxides with heavy metals in environment].

    PubMed

    Meng, You-Ting; Zheng, Yuan-Ming; Zhang, Li-Mei; He, Ji-Zheng

    2009-02-15

    Manganese (Mn) oxides are common minerals in natural environments that may play an important role in the biogeochemical cycles of heavy metals. Increasing evidences have shown that Mn (II) oxidation is a microbially-mediated process, and the Mn oxidizing microorganisms are thus recognized as the major drivers of the global Mn cycle. The major pathway for bacterial Mn (II) oxidation is catalysed by a multicopper oxidizing enzyme family. The primary Mn (IV) biooxides are phyllomanganate-like minerals most similar to delta-MnO2 or acid birnessite. Manganese oxides are known to have high sorption capacities for a wide variety of metal ions and considered to be the important environmental oxidant to many metal ions. This paper reviewed the mechanisms of biogenic manganese oxides formation and their reactions with heavy metal ions in environment.

  14. [Role of genetic factors in the formation of trace reactions in man].

    PubMed

    Mikheev, V F

    1979-01-01

    Trace processes due to presentation of visual nonverbal information, and the dynamics of the bioelectrical parameter (mean level of asymmetry of EEG-waves) were studies in 32 pairs of monozygote and 38 pairs of dizygote twins with twins method. Statistical processing of the data revealed a significant effect of genetic factors on the formation of individual variability of the characteristics of trace processes in humans. The results obtained showed that with increased functional load the intrapair similarity of trace reactions increased in monozygote twins and did not change or decrease in dizygote twins and in unrelated pairs. This fact is interpreted at a dependence of appearance of geneticly determined neurophysiological characteristics on the level of functional activity of the nervous system.

  15. 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

  16. A photoionization study of the formation of NO2/+/ by reaction of excited O2/+/ ions with NO

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; Rayermann, P.

    1977-01-01

    Photoionization mass spectrometer results are presented for the first observation of the ion-molecule reaction in which O2(+) + NO yields NO2(+) + O. The reaction is energetically possible for ground state O2(+) ions in the lowest vibrational level. Photoionization efficiency curves for NO(+), O2(+), and NO2(+) are presented and compared, with special emphasis on autoionization features. In addition to the production of NO2(+) by the cited reaction, there is also a possibility for NO2(+) formation by the process O2 + NO(+) yielding NO2(+) + O. This reaction is calculated to be exothermic for incident photon energies of 11.73 eV.

  17. 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.

  18. Geodynamic formation conditions of Early Cambrian lavas in the Ozernaya zone of Mongolia

    NASA Astrophysics Data System (ADS)

    Kovalenko, D. V.; Mongush, A. A.; Sath, H. N.

    2016-08-01

    Four types of pre-accretionary Early Cambrian lava sequences are distinguishable in the geological structure of the Ozernaya zone in western Mongolia: (I) close to N-MORB; (II) close to E-MORB; (III) enriched with trace elements and with HFSE minimums; (IV) depleted in trace elements and with HFSE minimums. All these lavas could have been formed in an island-arc‒back-arc basin system. N-MORB basalts were melted from depleted magma sources with c ɛNd( t) = 10.0-11.5. Plume melts originated from mantle sources with ɛNd( t) = 4.8-9.7. The sources of island arc lavas were characterized by ɛNd( t) = 7.3-9.9.

  19. Novel thermal effect at nanoshell heating by pulsed laser irradiation: hoop-shaped hot zone formation.

    PubMed

    Avetisyan, Yuri A; Yakunin, Alexander N; Tuchin, Valery V

    2012-10-01

    Photonic nanotechnologies have good perspectives to be widely used in biophotonics. In this study we have developed an approach for calculation of nanoparticle temperature field accounting for absorbed local intensity at pulse laser radiation of composite spherical nanoparticles (nanoshells). This approach allowed us to analyze spatial inhomogeneities of light field diffracted into a nanoshell and corresponding distribution of the absorption energy and to provide numerical solution of time-dependent heat conduction equation accounting for corresponding spatially inhomogeneous distribution of heating sources. We were able to predict the appearance of a novel thermal effect - hoop-shaped hot zone on the nanoshell surface. The observed effect has potential applications in cell biology and medicine for controlled cell optoporation and nanosurgery, as well as cancer cell killing.

  20. 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.

  1. 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.

  2. Formation of rutile fasciculate zone induced by sunlight irradiation at room temperature and its hemocompatibility.

    PubMed

    Zhang, Xuan-Hui; Zheng, Xiang; Cheng, Yuan; Li, Guo-Hua; Chen, Xiao-Ping; Zheng, Jian-Hui

    2013-08-01

    The fasciculate zone of phase pure rutile was fabricated under sunlight irradiation at room temperature, using titanium tetrachloride as a sole precursor. The crystal phase, morphology and microstructure, and optical absorption behavior of the samples were characterized by X-ray Diffraction, High-Resolution Transmission Electron Microscope (HRTEM) and UV-vis Diffuse Reflectance Spectra (DRS), respectively. XRD results show that the crystal phase of the sample is composed of rutile only, and a lattice distortion displays in the crystallite of the sample. HRTEM results show that the morphology of rutile particle is fasciculate zone constituted of nanoparticles with a diameter of 4-7 nm, and these particles grow one by one and step by step. The pattern of the selected area electron diffraction of the sample is Kikuchi type, which can be attributed to the predominant orientation growth of rutile nanoparticles along [001] induced by sunlight irradiation. DRS results show that the absorption threshold of the sample is 415 nm, corresponding to the band gap energy of 2.99 eV, which is lower than the band gap energy of rutile, 3.03 eV. Blood compatibility measurement shows that the sample has no remarkable effect on hemolytic and coagulation activity. The percent hemolysis of red blood cells is less than 5% even treated with a big dosage of the fasciculate rutile and under UV irradiation, and there are no obvious changes of plasma recalcification time after the rutile treatment. Thus, the novel structure of rutile fasciculate has low potential toxicity for blood and is hemocompatibility safe. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Modeling the formation of N-nitrosodimethylamine (NDMA) from the reaction of natural organic matter (NOM) with monochloramine.

    PubMed

    Chen, Zhuo; Valentine, Richard L

    2006-12-01

    This paper presents mechanistic studies on the formation of NDMA, a newly identified chloramination disinfection byproduct, from reactions of monochloramine with natural organic matter. A kinetic model was developed to validate proposed reactions and to predict NDMA formation in chloraminated water during the time frame of 1-5 days. This involved incorporating NDMA formation reactions into an established comprehensive model describing the oxidation of humic-type natural organic matter by monochloramine. A rate-limiting step involving the oxidation of NOM is theorized to control the rate of NDMA formation which is assumed to be proportional to the rate of NOM oxidized by monochloramine. The applicability of the model to describe NDMA formation in the presence of three NOM sources over a wide range in water quality (i.e., pH, DOC, and ammonia concentrations) was evaluated. Results show that with accurate measurement of monochloramine demand for a specific supply, NDMA formation could be modeled over an extended range of experimental conditions by considering a single NOM source-specific value of thetaNDMA, a stoichiometric coefficient relating the amount of NDMA produced to the amount of NOM oxidized, and several kinetic parameters describing NOM oxidation. Furthermore, the oxidation of NOM is the rate-limiting step governing NDMA formation. This suggests that NDMA formation over a 1-5 day time frame may be estimated from information on the chloramine or free chlorine demand of the NOM and the source-specific linear relationship between this demand and NDMA formation. Although the proposed model has not yet been validated for shorter time periods that may better characterize the residence time in some distribution systems, the improved understanding of the important reactions governing NDMA formation and the resulting model should benefit the water treatment industry as a tool in developing strategies that minimize NDMA formation.

  4. A macroscopic reaction: direct covalent bond formation between materials using a Suzuki-Miyaura cross-coupling reaction.

    PubMed

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

    2014-09-18

    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.

  5. 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.

    2011-01-11

    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) 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 (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.

  6. 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

  7. Efficient and directed peptide bond formation in the gas phase via ion/ion reactions.

    PubMed

    McGee, William M; McLuckey, Scott A

    2014-01-28

    Amide linkages are among the most important chemical bonds in living systems, constituting the connections between amino acids in peptides and proteins. We demonstrate the controlled formation of amide bonds between amino acids or peptides in the gas phase using ion/ion reactions in a mass spectrometer. Individual amino acids or peptides can be prepared as reagents by (i) incorporating gas phase-labile protecting groups to silence otherwise reactive functional groups, such as the N terminus; (ii) converting the carboxyl groups to the active ester of N-hydroxysuccinimide; and (iii) incorporating a charge site. Protonation renders basic sites (nucleophiles) unreactive toward the N-hydroxysuccinimide ester reagents, resulting in sites with the greatest gas phase basicities being, in large part, unreactive. The N-terminal amines of most naturally occurring amino acids have lower gas phase basicities than the side chains of the basic amino acids (i.e., those of histidine, lysine, or arginine). Therefore, reagents may be directed to the N terminus of an existing "anchor" peptide to form an amide bond by protonating the anchor peptide's basic residues, while leaving the N-terminal amine unprotonated and therefore reactive. Reaction efficiencies of greater than 30% have been observed. We propose this method as a step toward the controlled synthesis of peptides in the gas phase.

  8. Formation of Pd/Au Nanostructures from Pd Nanowires via Galvanic Replacement Reaction

    SciTech Connect

    Teng,X.; Wang, Q.; Liu, P.; Han, W.; Frenkel, A.; Wen, W.; Marinkovic, N.; Hanson, J.; Rodriguez, J.

    2008-01-01

    Bimetallic nanostructures with non-random metal atoms distribution are very important for various applications. To synthesize such structures via benign wet chemistry approach remains challenging. This paper reports a synthesis of a Au/Pd alloy nanostructure through the galvanic replacement reaction between Pd ultrathin nanowires (2.4 {+-} 0.2 nm in width, over 30 nm in length) and AuCl3 in toluene. Both morphological and structural changes were monitored during the reaction up to 10 h. Continuous changes of chemical composition and crystalline structure from Pd nanowires to Pd68Au32 and Pd45Au55 alloys, and to Au nanoparticles were observed. More interestingly, by using combined techniques such as high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS), UV-vis absorption, and extended X-ray absorption fine structure (EXAFS) spectroscopy, we found the formation of Pd68Au32 non-random alloy with Au-rich core and Pd-rich shell, and random Pd45Au55 alloy with uniformly mixed Pd and Au atom inside the nanoparticles, respectively. Density functional theory (DFT) calculations indicated that alkylamine will strongly stabilize Pd to the surface, resulting in diffusion of Au atoms into the core region to form a non-random alloy. We believe such benign synthetic techniques can also enable the large scale preparation of various types of non-random alloys for several technically important catalysis applications.

  9. Coupled chemical reactions in dynamic nanometric confinement: Ag2O membrane formation during ion track etching

    NASA Astrophysics Data System (ADS)

    Muñoz Hernandez, G.; Cruz, S. A.; Quintero, R.; García Arellano, H.; Fink, D.; Alfonta, L.; Mandabi, Y.; Kiv, A.; Vacik, J.

    2013-09-01

    In this study, continuous swift heavy ion tracks in thin polymer foils were etched from both sides to create two conical nanopores opposing each other. Shortly before both cones merged, one of the nanopores was filled with a silver salt solution, whereas etching of the other cone continued. At the moment of track breakthrough, the etchant reacted with the silver salt solution by forming an impermeable and insulating membrane. Continued etching around the thus-created obstacle led to repetitive {etchant - silver salt solution} interactions. The coupling of the two chemical reactions, {etchant - polymer} and {etchant - silver salt solution}, within the confinement of etched tracks, with continuously changing shapes, showed a highly dynamic nature as recorded by measuring both the electrical current and the optical transmission across the foils. At low etching speeds, a central membrane that grew in radius and thickness with time until, at a critical thickness, the membrane became rather impermeable was formed. However, at high etching speeds, the emerging reaction products exhibited a sponge-like consistency, which allowed for their infinite growth. This precipitation was accompanied by a pronounced current spike formation. A simple theoretical model explains, at a minimum, the basic features.

  10. Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: covalent bond formation.

    PubMed

    Ghirga, Francesca; D'Acquarica, Ilaria; Delle Monache, Giuliano; Mannina, Luisa; Molinaro, Carmela; Nevola, Laura; Sobolev, Anatoly P; Pierini, Marco; Botta, Bruno

    2013-07-19

    Resorc[4]arenes 1 and 2, which previously proved to entrap NO(+) cation within their cavities under conditions of host-to-guest excess, were treated with a 10-fold excess of NOBF4 salt in chloroform. Kinetic and spectral UV-visible analyses revealed the formation of isomeric 1:2 complexes as a direct evolution of the previously observed event. Accordingly, three-body 1-(NO(+))2 and 2-(NO(+))2 adducts were built by MM and fully optimized by DFT calculations at the B3LYP/6-31G(d) level of theory. Notably, covalent nitration products 4, 5 and 6, 7 were obtained by reaction of NOBF4 salt with host 1 and 2, respectively, involving macrocycle ring-opening and insertion of a nitro group in one of the four aromatic rings. In particular, compounds 4 and 6, both containing a trans-double bond in the place of the methine bridge, were oxidized to aldehydes 5 and 7, respectively, after addition of water to the reaction mixture. Calculation of the charge and frontier orbitals of the aromatic donor (HOMO) and the NO(+) acceptor (LUMO) clearly suggests an ipso electrophilic attack by a first NO(+) unit on the resorcinol ring, mediated by the second NO(+) unit.

  11. Formation of early and advanced Maillard reaction products correlates to the ripening of cheese.

    PubMed

    Spanneberg, Robert; Salzwedel, Grit; Glomb, Marcus A

    2012-01-18

    The present study deals with the characterization of the ripening of cheese. A traditional German acid curd cheese was ripened under defined conditions at elevated temperature, and protein and amino acid modifications were investigated. Degree of proteolysis and analysis of early [Amadori compound furosine (6)] and advanced [N(ε)-carboxymethyllysine (4), N(ε)-carboxyethyllysine (5)] Maillard reaction products confirmed the maturation to proceed from the rind to the core of the cheese. Whereas 6 was decreased, 4 and 5 increased over time. Deeper insight into the Maillard reaction during the ripening of cheese was achieved by the determination of selected α-dicarbonyl compounds. Especially methylglyoxal (2) showed a characteristic behavior during storage of the acid curd cheese. Decrease of this reactive structure was directly correlated to the formation of 5. To extend the results of experimental ripening to commercial cheeses, different aged Gouda types were investigated. Maturation times of the samples ranged from 6 to 8 weeks (young) to more than 1 year (aged). Again, increase of 5 and decrease of 2 were able to describe the ripening of this rennet coagulated cheese. Therefore, both chemical parameters are potent markers to characterize the degree of maturation, independent of coagulation.

  12. Numerical modelling of lithospheric flexure at subduction zones: what controls the formation of petit-spot volcanoes?

    NASA Astrophysics Data System (ADS)

    Bessat, Annelore; Pilet, Sébastien; Duretz, Thibault; Schmalholz, Stefan M.

    2017-04-01

    Petit-spot volcanoes were discovered fifteen years ago by Japanese researchers at the top of the down going plate in front of Japan (1). The location of these small lava flows is unusual, and seems related to the plate flexure in front of the subduction zone. Their formation seems, therefore, not to correspond to any classical type of volcanism such as MORB generation at mid ocean ridges, arc volcanism in subduction zones or intraplate volcanoes classically associated to deep mantle plumes. The discovery of petit-spot volcanoes is of great significance as it demonstrates, for the first time, that tectonic processes could generate intraplate volcanism and supports the existence of small-degree melts at the base of the lithosphere. First models for the formation of petit-spot volcanoes suggest that plate bending produces extension at the base of the lithosphere, thus allowing large cracks to propagate across the lithosphere. These cracks promote the extraction of low degree melts from the base of the lithosphere (2). However, the study of petit-spot mantle xenoliths from Japan (3) demonstrates that low degree melts are not directly extracted to the surface, but percolate and metasomatize the oceanic lithosphere. The aim of this study is to better understand the physical processes associated with the formation of petit-spot volcanoes. These thermo-mechanical processes will be studied using upper-mantle scale numerical simulations based on a 2D finite difference code. The numerical model considers viscoelastoplastic deformation; combination of laboratory-derived flow laws (e.g. diffusion and dislocation creep, Peierls creep) and heat transfer. The first step is to quantify the deformation processes that occur in the lithosphere and at the Lithosphere-Asthenosphere Boundary (LAB). The aims are to investigate, in particular, extensional deformation at the base of the lithosphere which is induced by plate flexure in front of a subduction zone. This study focuses on

  13. 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.

  14. Reaction pathways to CuInSe{sub 2} formation from electrodeposited precursors

    SciTech Connect

    Guillen, C.; Herrero, J.

    1995-06-01

    CuInSe{sub 2} thin films have been obtained from different precursors prepared by direct or sequential electrodeposition processes. The nature of the as-deposited layers and the evolution of the films during the heat-treatment in an inert (vacuum) or a reactive (elemental Se vapor) atmosphere have been studied by X-ray diffraction and X-ray photoelectron spectroscopy analysis. The chemistry of the different phase transformations occurring as a function of the annealing temperature has been examined, and possible reaction pathways for the formation of CuInSe{sub 2} are presented. The results show that high crystalline chalcopyrite CuInSe{sub 2} films with the desired composition can be obtained after annealing either direct or sequentially electrodeposited precursors at 400 C. An improvement in film quality can be gained by using an electrodeposited Cu layer as growth surface for the CuInSe{sub 2} formation. If elemental Se is also added during the heat-treatment, then a higher recrystallization of the films is observed.

  15. Photochemical reactions of divalent mercury with thioglycolic acid: formation of mercuric sulfide particles.

    PubMed

    Si, Lin; Ariya, Parisa A

    2015-01-01

    Mercury (Hg) is a key toxic global pollutant. Studies in aquatic environment have suggested that thiols could be important for mercury speciation. Thioglycolic acid has been detected in various natural water systems and used as a model compound to study the complicated interaction between mercury and polyfunctional dissolved organic matter (DOM). We herein presented the first evidence for mercury particle formation during kinetic and product studies on the photochemistry of divalent mercury (Hg(2+)) with thioglycolic acid at near environmental conditions. Mercuric sulfide (HgS) particles formed upon photolysis were identified by high-resolution transmission electron microscopy coupled with energy dispersive spectrometry and select area electron diffraction. Kinetic data were obtained using UV-visible spectrophotometry and cold vapour atomic fluorescent spectrometry. The apparent first-order reaction rate constant under our experimental conditions was calculated to be (2.3±0.4)×10(-5) s(-1) at T=296±2 K and pH 4.0. It was found that (89±3)% of the reactants undergo photoreduction to generate elemental mercury (Hg(0)). The effects of ionic strengths, pH and potassium ion were also investigated. The formation of HgS particles pointed to the possible involvement of heterogeneous processes. Our kinetic results indicated the importance of weak binding sites on DOM to Hg in photoreduction of Hg(2+) to Hg(0). The potential implications of our data on environmental mercury transformation were discussed.

  16. Turing pattern formation in the chlorine dioxide-iodine- malonic acid reaction-diffusion system

    NASA Astrophysics Data System (ADS)

    Setayeshgar, Sima

    The formation of localized structures in the chlorine dioxide-idodine-malonic acid (CDIMA) reaction-diffusion system is investigated numerically using a realistic model of this system. We analyze the one-dimensional patterns formed along the gradients imposed by boundary feeds, and study their linear stability to symmetry- breaking perturbations (the Turing instability) in the plane transverse to these gradients. We establish that an often-invoked simple local linear analysis which neglects longitudinal diffusion is inappropriate for predicting the linear stability of these patterns. Using a fully nonuniform analysis, we investigate the structure of the patterns formed along the gradients and their stability to transverse Turing pattern formation as a function of the values of two control parameters: the malonic acid feed concentration and the size of the reactor in the dimension along the gradients. The results from this investigation are compared with existing experimental results. We also verify that the two-variable reduction of the chemical model employed in the linear stability analysis is justified. Finally, we present numerical solution of the CDIMA system in two dimensions which is in qualitative agreement with experiments. This result also confirms our linear stability analysis, while demonstrating the feasibility of numerical exploration of realistic chemical models.

  17. Condensation reactions and formation of amides, esters, and nitriles under hydrothermal conditions.

    PubMed

    Rushdi, Ahmed I; Simoneit, Bernd R T

    2004-01-01

    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 degrees 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.

  18. Metal ion complex formation in small lakes of the Western Siberian Arctic zone

    NASA Astrophysics Data System (ADS)

    Kremleva, Tatiana; Dinu, Marina

    2017-04-01

    be predominantly in free, ionic or bound form with inorganic ligands. This state means paradox consequence that the increase of dissolved Fe content will lead to toxicity rise of other elements having less affinity to organic material. For surface waters of Western Siberian Arctic zone this situation is quite common. The total concentration of iron and aluminum ions in most lakes of tundra and northern taiga zones is approximately equal to water complexing ability. From the other side humic substances participation in inactivation of other more toxic metals (Cu, Pb, Cd, Cr, Ni et al.) will be poor. Arctic part of Western Siberia undergoes significant anthropogenic load due to extensive oil and gas recovery in this zone. Surface waters of Western Siberia are characterized by high natural content of iron, aluminum and copper ions and anthropogenic load of heavy metals makes the situation more serious.

  19. The formation and chemistry of low degree hydrous partial melt on top of the transition zone

    NASA Astrophysics Data System (ADS)

    Frost, Daniel J.; Mookherjee, Mainak

    2010-05-01

    There is some geophysical evidence for the presence of silicate melt on top of the 410 km seismic discontinuity. It has also been argued that the difference in the water storage capacity of upper mantle versus transition zone minerals may cause dehydration melting as material up-wells across the 410. Studies have proposed that hydrous partial melts may be neutrally buoyant in the mantle at these conditions. In order to assess these possibilities it is important to determine the likely composition of small degree hydrous melts at these conditions and to measure the H2O contents of mantle minerals coexisting with this melt phase. The composition of a hydrous melt in equilibrium with a mantle peridotite composition has been determined at conditions of the 410 and 1450°C. Sandwich experiments were performed where an 'initial-guess' hydrous melt composition was equilibrated with 50% anhydrous peridotite. The resulting melt composition was used to assemble a further melt, which was then equilibrated in the same way. After several iterations it was possible to derive a melt composition, which was in equilibrium with a mineral assemblage identical to that observed for an anhydrous peridotite composition at the same conditions. We assess whether this melt composition could be neutrally buoyant at 410km. The 410 km discontinuity may also correspond to a transition in redox state in the mantle from a reducing transition zone to a less reduced upper mantle. Volatiles may also collect and induce melting at this horizon due to the oxidation of a rising mobile reduced fluid phase containing CH4. Minerals in mantle upwelling out of a hydrous melt layer would be expected to have H2O contents close to saturation; however, this may not be the case if the melt layer also contains other volatile components such as CO2 or CH4, which further lower the H2O activity in the melt. We assess ranges of melt compositions that may be in equilibrium with minerals containing relatively low H2O

  20. 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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. 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

  3. Effect of oxygen minimum zone formation on communities of marine protists

    PubMed Central

    Orsi, William; Song, Young C; Hallam, Steven; Edgcomb, Virginia

    2012-01-01

    Changes in ocean temperature and circulation patterns compounded by human activities are leading to oxygen minimum zone (OMZ) expansion with concomitant alteration in nutrient and climate active trace gas cycling. Here, we report the response of microbial eukaryote populations to seasonal changes in water column oxygen-deficiency using Saanich Inlet, a seasonally anoxic fjord on the coast of Vancouver Island British Columbia, as a model ecosystem. We combine small subunit ribosomal RNA gene sequencing approaches with multivariate statistical methods to reveal shifts in operational taxonomic units during successive stages of seasonal stratification and renewal. A meta-analysis is used to identify common and unique patterns of community composition between Saanich Inlet and the anoxic/sulfidic Cariaco Basin (Venezuela) and Framvaren Fjord (Norway) to show shared and unique responses of microbial eukaryotes to oxygen and sulfide in these three environments. Our analyses also reveal temporal fluctuations in rare populations of microbial eukaryotes, particularly anaerobic ciliates, that may be of significant importance to the biogeochemical cycling of methane in OMZs. PMID:22402396

  4. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji.

    PubMed

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun

    2015-01-01

    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, P<0.01). We have shown for the first time that aldimine (LX1c) formation reaction might be enhanced in Hb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction.

  5. Detecting transmissive bedrock fracture zones under cover of glacial formations using residential water-well production data

    NASA Astrophysics Data System (ADS)

    Maharjan, Madan; Eckstein, Yoram

    2013-12-01

    Tracing fractures under glacial drift commonly involves costly and often unfeasible (in populated areas) geophysical methods or outcrop surveys, often far from the area of interest. A hypothesis is tested, that the specific capacity data for wells penetrating through glacial drift into a bedrock aquifer display two statistical populations: assuming uniform well construction, the wells with high specific capacity penetrate transmissive fracture zones, while those with low specific capacity encounter non-fractured rock characterized by primary porosity. The hypothesis was tested on 617 wells drilled into the Pennsylvanian Sharon Sandstone, Geauga County, Ohio (USA). Hydraulic conductivity, calculated using the Cooper and Jacob (1946) approximation to Theis' non-equilibrium radial flow equation, followed quasi-log-normal distribution (geometric mean 9.88 × 10-6 m/s). The lower values presumably correspond to primary porosity, and higher values correspond to bedrock fracture zones. The higher hydraulic conductivity followed two distinct orientations (N34°E, N44°W), corresponding with the regional fracture pattern of the Allegheny Plateau. A variogram showed that the wells within a kilometer of each other correlate and that wells penetrating the thicker glacial blanket have lower hydraulic conductivity and larger drawdown. Cooper and Jacob (1946) A generalized graphical method for evaluating formation constants and summarizing well-field history, Am. Geoph. Union Trans. 27/4:526-534.

  6. Late Hesperian plains formation and degradation in a low sedimentation zone of the northern lowlands of Mars

    NASA Astrophysics Data System (ADS)

    Rodríguez, José Alexis Palmero; Tanaka, Kenneth L.; Berman, Daniel C.; Kargel, Jeffrey S.

    2010-11-01

    The plains materials that form the martian northern lowlands suggest large-scale sedimentation in this part of the planet. The general view is that these sedimentary materials were transported from zones of highland erosion via outflow channels and other fluvial systems. The study region, the northern circum-polar plains south of Gemini Scopuli on Planum Boreum, comprises the only extensive zone in the martian northern lowlands that does not include sub-basin floors nor is downstream from outflow channel systems. Therefore, within this zone, the ponding of fluids and fluidized sediments associated with outflow channel discharges is less likely to have taken place relative to sub-basin areas that form the other northern circum-polar plains surrounding Planum Boreum. Our findings indicate that during the Late Hesperian sedimentary deposits produced by the erosion of an ancient cratered landscape, as well as via sedimentary volcanism, were regionally emplaced to form extensive plains materials within the study region. The distribution and magnitude of surface degradation suggest that groundwater emergence from an aquifer that extended from the Arabia Terra cratered highlands to the northern lowlands took place non-catastrophically and regionally within the study region through faulted upper crustal materials. In our model the margin of the Utopia basin adjacent to the study region may have acted as a boundary to this aquifer. Partial destruction and dehydration of these Late Hesperian plains, perhaps induced by high thermal anomalies resulting from the low thermal conductivity of these materials, led to the formation of extensive knobby fields and pedestal craters. During the Early Amazonian, the rates of regional resurfacing within the study region decreased significantly; perhaps because the knobby ridges forming the eroded impact crater rims and contractional ridges consisted of thermally conductive indurated materials, thereby inducing freezing of the tectonically

  7. Late Hesperian plains formation and degradation in a low sedimentation zone of the northern lowlands of Mars

    USGS Publications Warehouse

    Rodriguez, J.A.P.; Tanaka, K.L.; Berman, D.C.; Kargel, J.S.

    2010-01-01

    The plains materials that form the martian northern lowlands suggest large-scale sedimentation in this part of the planet. The general view is that these sedimentary materials were transported from zones of highland erosion via outflow channels and other fluvial systems. The study region, the northern circum-polar plains south of Gemini Scopuli on Planum Boreum, comprises the only extensive zone in the martian northern lowlands that does not include sub-basin floors nor is downstream from outflow channel systems. Therefore, within this zone, the ponding of fluids and fluidized sediments associated with outflow channel discharges is less likely to have taken place relative to sub-basin areas that form the other northern circum-polar plains surrounding Planum Boreum. Our findings indicate that during the Late Hesperian sedimentary deposits produced by the erosion of an ancient cratered landscape, as well as via sedimentary volcanism, were regionally emplaced to form extensive plains materials within the study region. The distribution and magnitude of surface degradation suggest that groundwater emergence from an aquifer that extended from the Arabia Terra cratered highlands to the northern lowlands took place non-catastrophically and regionally within the study region through faulted upper crustal materials. In our model the margin of the Utopia basin adjacent to the study region may have acted as a boundary to this aquifer. Partial destruction and dehydration of these Late Hesperian plains, perhaps induced by high thermal anomalies resulting from the low thermal conductivity of these materials, led to the formation of extensive knobby fields and pedestal craters. During the Early Amazonian, the rates of regional resurfacing within the study region decreased significantly; perhaps because the knobby ridges forming the eroded impact crater rims and contractional ridges consisted of thermally conductive indurated materials, thereby inducing freezing of the tectonically

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

    NASA Technical Reports Server (NTRS)

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

    2017-01-01

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

  9. N-nitrosoamine and N-nitroamine formation: factors influencing the aqueous reactions of nitrogen dioxide with morpholine

    SciTech Connect

    Cooney, R.V.; Ross, P.D.; Bartolini, G.L.; Ramseyer, J.

    1987-01-01

    The formation of nitrosamine and nitroamine from low levels of nitrogen dioxide (1-99 ppm) and morpholine in aqueous solution was examined. We have shown for the first time that significant quantities of N-nitromorpholine form at physiological pH; the rate of N-nitration was more than double that of N-nitrosation at 37/sup 0/C, pH 7.4. The effects of temperature, pH, reactant concentration, and various anions on both nitration and nitrosation reactions are presented. In addition to pH effects, a deuterium effect was observed for the nitration reaction, suggesting that hydrogen abstraction is a rate-limiting step in product formation. Possible reaction mechanisms are described, and the implications for carcinogen formation in vivo due to low-level NO/sub 2/ exposure are discussed. 16 references, 7 figures, 4 tables.

  10. Formation of lithospheric shear zones: Effect of temperature on two-phase grain damage

    NASA Astrophysics Data System (ADS)

    Mulyukova, Elvira; Bercovici, David

    2017-09-01

    depth of a single shear zone.

  11. 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

  12. On the formation of acceleration and reaction-diffusion wavefronts in autocatalytic-type reaction-diffusion systems

    NASA Astrophysics Data System (ADS)

    Needham, D. J.

    2006-06-01

    We consider generalization of the theory for the evolution of reaction-diffusion and accelerating wavefronts in KPP-type systems as developed in Needham (2004, Proc. R. Soc. Lond. A, 460, 1921-1934) (DN). These generalizations allow for the removal of a number of technical restrictions imposed in the paper of DN.

  13. Discrete approximations of detonation flows with structured detonation reaction zones by discontinuous front models: A program burn algorithm based on detonation shock dynamics

    SciTech Connect

    Bdzil, J.B.; Jackson, T.L.; Stewart, D.S.

    1999-02-02

    In the design of explosive systems the generic problem that one must consider is the propagation of a well-developed detonation wave sweeping through an explosive charge with a complex shape. At a given instant of time the lead detonation shock is a surface that occupies a region of the explosive and has a dimension that is characteristic of the explosive device, typically on the scale of meters. The detonation shock is powered by a detonation reaction zone, sitting immediately behind the shock, which is on the scale of 1 millimeter or less. Thus, the ratio of the reaction zone thickness to the device dimension is of the order of 1/1,000 or less. This scale disparity can lead to great difficulties in computing three-dimensional detonation dynamics. An attack on the dilemma for the computation of detonation systems has lead to the invention of sub-scale models for a propagating detonation front that they refer to herein as program burn models. The program burn model seeks not to resolve the fine scale of the reaction zone in the sense of a DNS simulation. The goal of a program burn simulation is to resolve the hydrodynamics in the inert product gases on a grid much coarser than that required to resolve a physical reaction zone. The authors first show that traditional program burn algorithms for detonation hydrocodes used for explosive design are inconsistent and yield incorrect shock dynamic behavior. To overcome these inconsistencies, they are developing a new class of program burn models based on detonation shock dynamic (DSD) theory. It is hoped that this new class will yield a consistent and robust algorithm which reflects the correct shock dynamic behavior.

  14. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    PubMed

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  15. 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

  16. 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

  17. Quantum chemical approach for condensed-phase thermochemistry (II): Applications to formation and combustion reactions of liquid organic molecules

    NASA Astrophysics Data System (ADS)

    Ishikawa, Atsushi; Nakai, Hiromi

    2015-03-01

    The harmonic solvation model (HSM), which was recently developed for evaluating condensed-phase thermodynamics by quantum chemical calculations (Nakai and Ishikawa, 2014), was applied to formation and combustion reactions of simple organic molecules. The conventional ideal gas model (IGM) considerably overestimated the entropies of the liquid molecules. The HSM could significantly improve this overestimation; mean absolute deviations for the Gibbs energies of the formation and combustion reactions were (49.6, 26.7) for the IGM and (9.7, 5.4) for the HSM in kJ/mol.

  18. Rapid gas hydrate formation process

    DOEpatents

    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.

  19. 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.

  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. Acrylamide formation from asparagine under low-moisture Maillard reaction conditions. 1. Physical and chemical aspects in crystalline model systems.

    PubMed

    Robert, Fabien; Vuataz, Gilles; Pollien, Philippe; Saucy, Françoise; Alonso, Maria-Isabelle; Bauwens, Isabelle; Blank, Imre

    2004-11-03

    The formation of acrylamide in crystalline model systems based on asparagine and reducing sugars was investigated under low-moisture reaction conditions. The acrylamide amounts were correlated with physical changes occurring during the reaction. Molecular mobility of the precursors turned out to be a critical parameter in solid systems, which is linked to the melting behavior and the release of crystallization water of the reaction sample. Heating binary mixtures of asparagine monohydrate and anhydrous reducing sugars led to higher acrylamide amounts in the presence of fructose compared to glucose. Differential scanning calorimetry measurements performed in open systems indicated melting of fructose at 126 degrees C, whereas glucose and galactose fused at 157 and 172 degrees C, respectively. However, glucose was the most reactive and fructose the least efficient sugar in anhydrous liquid systems, indicating that at given molecular mobility the chemical reactivity of the sugar was the major driver in acrylamide formation. Furthermore, reaction time and temperature were found to be covariant parameters: acrylamide was preferably formed by reacting glucose and asparagine at 120 degrees C for 60 min, whereas 160 degrees C was required at shorter reaction time (5 min). These results suggest that, in addition to the chemical reactivity of ingredients, their physical state as well as reaction temperature and time would influence the formation of acrylamide during food processing.

  2. Optimised formation of blue Maillard reaction products of xylose and glycine model systems and associated antioxidant activity.

    PubMed

    Yin, Zi; Sun, Qian; Zhang, Xi; Jing, Hao

    2014-05-01

    A blue colour can be formed in the xylose (Xyl) and glycine (Gly) Maillard reaction (MR) model system. However, there are fewer studies on the reaction conditions for the blue Maillard reaction products (MRPs). The objective of this study is to investigate characteristic colour formation and antioxidant activities in four different MR model systems and to determine the optimum reaction conditions for the blue colour formation in a Xyl-Gly MR model system, using the random centroid optimisation program. The blue colour with an absorbance peak at 630 nm appeared before browning in the Xyl-Gly MR model system, while no blue colour formation but only browning was observed in the xylose-alanine, xylose-aspartic acid and glucose-glycine MR model systems. The Xyl-Gly MR model system also showed higher antioxidant activity than the other three model systems. The optimum conditions for blue colour formation were as follows: xylose and glycine ratio 1:0.16 (M:M), 0.20 mol L⁻¹ NaHCO₃, 406.1 mL L⁻¹ ethanol, initial pH 8.63, 33.7°C for 22.06 h, which gave a much brighter blue colour and a higher peak at 630 nm. A characteristic blue colour could be formed in the Xyl-Gly MR model system and the optimum conditions for the blue colour formation were proposed and confirmed. © 2013 Society of Chemical Industry.

  3. Theoretical studies on C 2H+NO reactions: mechanism for HCN+CO and HCO+CN formation

    NASA Astrophysics Data System (ADS)

    Sengupta, Debasis; Peeters, Jozef; Nguyen, Minh Tho

    1998-01-01

    In order to investigate HCN+CO and/or HCO+CN formation during the reaction of the ethynyl radical with nitric oxide we explore the potential energy surface of [C 2HNO] isomers via density functional theory. Product formation takes place via several isomerization steps after the initial adduct formation. We identified one reaction pathway resulting in fragmentation that is accessible without activation of the initial reactants; this path forms HCN+CO and involves a four-membered cyclic structure. Other pathways, involving formyl cyanide and leading to HCN+CO and/or HCO+CN, require initial activation. Wherever possible, our calculated energies are compared with higher level ab initio results. The heat of formation of formyl cyanide is calculated to be 14.4 kcal/mol which compares reasonably well with the reported value of 11.6 kcal/mol at the G2 level of theory.

  4. 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.

    2013-09-01

    We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of different emission sources without limitation from the instruments or facilities available at any single site. 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 aging of emissions may be simulated over a range of temperatures (-7 to 25 °C). A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 s-1 was determined at 25 °C. We demonstrate the utility of this new system by presenting results on the aging (OH = 12 × 106 cm-3 h) of emissions from a modern (Euro 5) gasoline car operated during a driving cycle (New European Driving Cycle, NEDC) on a chassis dynamometer in a vehicle test cell. Emissions from the entire NEDC were sampled and aged in the chamber. Total organic aerosol (OA; primary organic aerosol (POA) emission + secondary organic aerosol (SOA) formation) was (369.8-397.5)10-3 g kg-1 fuel, or (13.2-15.4) × 10-3 g km-1, after aging, with aged OA/POA in the range 9-15. A thorough investigation of the composition of the gas phase emissions suggests that the observed SOA is from previously unconsidered precursors and processes. This large enhancement in particulate matter mass from gasoline vehicle aerosol emissions due to SOA formation, if it occurs across a wider range of gasoline vehicles, would have significant implications for our understanding of the contribution of on-road gasoline vehicles to ambient aerosols.

  5. Effects of vinyl series polymers on the formation of hematite particles in a forced hydrolysis reaction.

    PubMed

    Kandori, Kazuhiko; Yamoto, Yukihiro; Ishikawa, Tatsuo

    2005-03-15

    The influence of polymers on the formation of hematite particles from forced hydrolysis of acidic FeCl(3) solution was investigated using vinyl series polymers with different functional groups. The disk-like hematite particles were produced from forced hydrolysis of acidic FeCl(3) solution in the presence of polyvinyl alcohol (PVA: 0-1 wt%). On the other hand, spherical particles were produced by addition of very small amounts of polyacrylamide (PAAm: 0-0.004 wt%). The size of spherical particles was slightly decreased with increase in the concentration of PAAm. The ellipsoidal particles were precipitated by addition of a very low concentration of polyacrylic acid (PAAc: 0-0.004 wt%). The effect of polymers on the hematite particle formation was expressed in the order of PVAreaction sequence for the systems with polymers. A rotational particle preparation procedure suggested that the morphology of hematite particle is governed by the mode and strength of polymer adsorption onto beta-FeOOH and polynuclear primary particles.

  6. Thermodynamics of reactions of complex formation for Ce3+ and Er3+ ions with glycine in an aqueous solution

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Skvortsov, I. A.

    2017-06-01

    Enthalpies of complex formation for glycine (HL±) with Ce3+ and Er3+ ions at 298.15 K and the value of the ionic strength of 0.5 (KNO3) are determined by calorimetric means using two independent procedures. Thermodynamic characteristics of the reactions of formation for complexes of glycine with Ce3+ and Er3+ ions at various [metal]: [ligand] molar ratios are calculated.

  7. Thermodynamics of slush and snow-ice formation in the Antarctic sea-ice zone

    NASA Astrophysics Data System (ADS)

    Jutras, Mathilde; Vancoppenolle, Martin; Lourenço, Antonio; Vivier, Frédéric; Carnat, Gauthier; Madec, Gurvan; Rousset, Clément; Tison, Jean-Louis

    2016-09-01

    Snow over Antarctic sea ice is often flooded by brine or seawater, particularly in spring, forming slush and snow ice. Here, we evaluate the representation of the thermodynamics of slush and snow-ice formation in large-scale sea-ice models, using laboratory experiments (NaCl solutions poured into grated ice in an isolated container). Scaling analysis highlights latent heat as the main term of the energy budget. The temperature of the new sea ice immediately after flooding is found very close to the saltwater freezing point, whereas its bulk salinity is typically > 20 g / kg. Large-scale sea-ice models faithfully represent such physics, yet the uncertainty on the origin of flooding saltwater impacts the calculated new ice temperature, because of the different salinities of seawater and brine. The laboratory experiments also suggest a potential limitation to the existing physical representations of flooding: for brine fractions > 60 %, ice crystals start floating upon saltwater. Natural sea-ice observations suggest that the isolated system assumption holds for a few hours at most, after which rapid heat and salt exchanges mostly destroy the initial flooding signature on temperature and salinity. A small footprint on ice salinity remains however, natural snow ice is found 3-5 g/kg more saline than other forms of sea ice.

  8. Massive Formation of Equiaxed Crystals by Avalanches of Mushy Zone Segments

    NASA Astrophysics Data System (ADS)

    Ludwig, A.; Stefan-Kharicha, M.; Kharicha, A.; Wu, M.

    2017-06-01

    It is well known that the growth and motion of equiaxed crystals govern important microstructural features, especially in larger castings such as heavy ingots. To determine the origin of the equiaxed crystals, heterogeneous nucleation, and/or fragmentation of dendrite arms from columnar regions are often discussed. In the present study, we demonstrate that under certain conditions relatively large areas of mushy regions slide downward and form spectacular crystal avalanches. These avalanches crumble into thousands of dendritic fragments, whereby the larger fragments immediately sediment and the smaller proceed to behave as equiaxed crystals. Traces of such crystal avalanches can be seen by conspicuous equiaxed layers in the lower part of the casting. From the arguments in the discussion, it is believed that such a phenomenon may occur in alloys which reveal an upward solutal buoyancy in the interdendritic mush. This would include certain steels and other alloys such as Cu-Al, Pb-Sn, or Ni-Al-alloys. Moreover, the occurrence of crystal avalanches contribute to the formation of V-segregations.

  9. Massive Formation of Equiaxed Crystals by Avalanches of Mushy Zone Segments

    NASA Astrophysics Data System (ADS)

    Ludwig, A.; Stefan-Kharicha, M.; Kharicha, A.; Wu, M.

    2017-03-01

    It is well known that the growth and motion of equiaxed crystals govern important microstructural features, especially in larger castings such as heavy ingots. To determine the origin of the equiaxed crystals, heterogeneous nucleation, and/or fragmentation of dendrite arms from columnar regions are often discussed. In the present study, we demonstrate that under certain conditions relatively large areas of mushy regions slide downward and form spectacular crystal avalanches. These avalanches crumble into thousands of dendritic fragments, whereby the larger fragments immediately sediment and the smaller proceed to behave as equiaxed crystals. Traces of such crystal avalanches can be seen by conspicuous equiaxed layers in the lower part of the casting. From the arguments in the discussion, it is believed that such a phenomenon may occur in alloys which reveal an upward solutal buoyancy in the interdendritic mush. This would include certain steels and other alloys such as Cu-Al, Pb-Sn, or Ni-Al-alloys. Moreover, the occurrence of crystal avalanches contribute to the formation of V-segregations.

  10. 2-Formylcinnamaldehyde formation yield from the OH radical-initiated reaction of naphthalene: effect of NO(2) concentration.

    PubMed

    Nishino, Noriko; Arey, Janet; Atkinson, Roger

    2012-08-07

    Naphthalene, typically the most abundant polycyclic aromatic hydrocarbon in the atmosphere, reacts with OH radicals by addition to form OH-naphthalene adducts. These OH-naphthalene adducts react with O(2) and NO(2), with the two reactions being of equal importance in air at an NO(2) mixing ratio of ∼60 ppbv. 2-Formylcinnamaldehyde [o-HC(O)C(6)H(4)CH═CHCHO] is a major product of the OH radical-initiated reaction of naphthalene, with a yield from the reaction of OH-naphthalene adducts with NO(2) of ∼56%. We have measured, on a relative basis, the formation yield of 2-formylcinnamaldehyde from the OH radical-initiated reaction of naphthalene in air at average NO(2) concentrations of 1.2 × 10(11), 1.44 × 10(12), and 1.44 × 10(13) molecules cm(-3) (mixing ratios of 0.005, 0.06, and 0.6 ppmv, respectively). These NO(2) concentrations cover the range of conditions corresponding to the OH-naphthalene adducts reacting ∼90% of the time with O(2) to ∼90% of the time with NO(2). The 2-formylcinnamaldehyde formation yield decreased with decreasing NO(2) concentration, and a yield from the OH-naphthalene adducts + O(2) reaction of 14% is obtained based on a 56% yield from the OH-naphthalene adducts + NO(2) reaction. Based on previous measurements of glyoxal and phthaldialdehyde from the naphthalene + OH reaction and literature data for the OH radical-initiated reactions of monocyclic aromatic hydrocarbons, the reactions of OH-naphthalene adducts with O(2) appear to differ significantly from the OH-monocyclic adduct + O(2) reactions.

  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. Formation of Vibrationally Excited OH by the Reaction H + O(3).

    PubMed

    Charters, P E; Macdonald, R G; Polanyi, J C

    1971-08-01

    An earlier study [Chem. Phys. Lett. 1, 619 (1968)] concluded that the reaction H + O(3) ? OH + O(2) forms OH predominantly in the highest accessible vibrational levels, upsilon = 8 and 9. We have extended this earlier work (1) by using fourier transform spectroscopy which is capable of giving more precise values for the relative vibrational populations at low intensities, (2) by recording emission down to lower background pressures (1 x 10(-4) Torr), and (3) by treating the vessel walls so as to remove OHdagger (vibrationally excited OH in it ground (2)II electronic state) more effectively. This involved using a room temperature vessel coated with silica gel. Under these conditions (provided that the values available for the radiational lifetime of OHdagger are correct) vibrational relaxation of OHdagger should have been largely arrested. We conclude that the relative rate constants for formation of OHdagger in levels upsilon are k(upsilon = 6) < 0.4, k(upsilon = 7) asymptotically equal to 0.4, k(upsilon = 8) asymptotically equal to 0.8, and k(upsilon = 9) = 1.00.

  13. The effect of reactions on the formation and readout of the gradient of Bicoid

    NASA Astrophysics Data System (ADS)

    Perez Ipiña, Emiliano; Ponce Dawson, Silvina

    2017-02-01

    During early development, the establishment of gradients of transcriptional factors determines the patterning of cell fates. The case of Bicoid (Bcd) in Drosophila melanogaster embryos is well documented and studied. There are still controversies as to whether SDD models in which Bcd is Synthesized at one end, then Diffuses and is Degraded can explain the gradient formation within the timescale observed experimentally. The Bcd gradient is observed in embryos that express a Bicoid-eGFP fusion protein (Bcd-GFP) which cannot differentiate if Bcd is freely diffusing or bound to immobile sites. In this work we analyze an SDID model that includes the Interaction of Bcd with binding sites. We simulate numerically the resulting full reaction-diffusion system in a cylindrical domain using previously determined biophysical parameters and a simplified version of the Bcd source. In this way we obtain solutions that depend on the spatial location approximately as observed experimentally and that reach such dependence at a time that is also compatible with the experimental observations. Analyzing the differences between the free and bound Bcd distributions we observe that the latter spans over a longer lengthscale. We conclude that deriving the lengthscale from the distribution of Bcd-GFP can lead to an overestimation of the gradient lengthscale and of the Hill coefficient that relates the concentrations of Bcd and of the protein, Hunchback, whose production is regulated by Bcd.

  14. Effects of amino acids on the formation of hematite particles in a forced hydrolysis reaction.

    PubMed

    Kandori, Kazuhiko; Sakai, Masaji; Inoue, Shoko; Ishikawa, Tatsuo

    2006-01-01

    The influence of amino acids on the formation of hematite particles from a forced hydrolysis reaction of acidic FeCl3 solution was examined. The spherical particles were produced on the systems with L-phenylalanine (L-Phe), L-serine (L-Ser) and L-alanine (L-Ala), though L-glutamine (L-Gln) and L-glutamic acid (L-Glu) gave ellipsoidal hematite particles. This morphological change in hematite particles is consistent with the order of stability constant of amino acids against to Fe3+ ions (K). The hematite particles produced with L-Glu, L-Gln and L-Ser were highly porous because they are formed by aggregation of cluster particles. These particles exhibited microporous behavior by outgassing the particles below 200 degrees C while they changed to mesoporous after treating above 300 degrees C by elimination of amino acids molecules remained between the cluster particles within the hematite particles. The hematite particles strongly depended on the nature of amino acids such as alternation of solution pH and adsorption affinity to beta-FeOOH and/or polynuclear primary (PN) particles. The systems on L-Ala and L-Phe, showing very rapid phase transformation from beta-FeOOH to hematite, exhibited the Ostwald ripening. A rotational particle preparation procedure suggested that the morphology of hematite particle is governed by the mode and strength of amino acid adsorption onto beta-FeOOH and/or PN particles.

  15. 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.

  16. The effect of reactions on the formation and readout of the gradient of Bicoid.

    PubMed

    Ipiña, Emiliano Perez; Dawson, Silvina Ponce

    2017-02-08

    During early development, the establishment of gradients of transcriptional factors determines the patterning of cell fates. The case of Bicoid (Bcd) in Drosophila melanogaster embryos is well documented and studied. There are still controversies as to whether SDD models in which Bcd is Synthesized at one end, then Diffuses and is Degraded can explain the gradient formation within the timescale observed experimentally. The Bcd gradient is observed in embryos that express a Bicoid-eGFP fusion protein (Bcd-GFP) which cannot differentiate if Bcd is freely diffusing or bound to immobile sites. In this work we analyze an SDID model that includes the Interaction of Bcd with binding sites. We simulate numerically the resulting full reaction-diffusion system in a cylindrical domain using previously determined biophysical parameters and a simplified version of the Bcd source. In this way we obtain solutions that depend on the spatial location approximately as observed experimentally and that reach such dependence at a time that is also compatible with the experimental observations. Analyzing the differences between the free and bound Bcd distributions we observe that the latter spans over a longer lengthscale. We conclude that deriving the lengthscale from the distribution of Bcd-GFP can lead to an overestimation of the gradient lengthscale and of the Hill coefficient that relates the concentrations of Bcd and of the protein, Hunchback, whose production is regulated by Bcd.

  17. 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.

  18. 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

  19. 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...

  20. 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...

  1. Effects of the pouring temperature on the formation of the bonding zone between AZ91 and AlSi17 in the compound casting process

    NASA Astrophysics Data System (ADS)

    Mola, R.; Bucki, T.; Dziadoń, A.

    2017-02-01

    The compound casting process was used to join AZ91 magnesium alloy to AlSi17 aluminium alloy. Liquid AZ91 was poured onto a solid AlSi17 insert placed in a steel mould heated to 370 °C. The experimental results showed that the temperature of the AZ91 melt affected the formation of the bonding zone between the two alloys. A continuous bonding zone was formed by applying a pouring temperature of 650 °C. The use of higher temperatures, i.e. 680 °C and 700 °C, did not lead to the formation of a continuous metallurgical transition zone at the AZ91/AlSi17 interface. The bonding zone was analysed using an optical microscope and a scanning electron microscope equipped with an energy dispersive X-ray (EDS) detector. The structural constituents of the bonding zone near the AlSi17 alloy were: an Al3Mg2 intermetallic phase, primary Si particles surrounded by a rim of an Mg2Si intermetallic phase and fine Mg2Si particles. The area of the bonding zone that was adjacent to the AZ91 alloy had a eutectic structure composed of an Mg17Al12 intermetallic phase and a solid solution of Al and Si in Mg.

  2. Reaction of Ynamides with Iminoiodinane-Derived Nitrenes: Formation of Oxazolones and Polyfunctionalized Oxazolidinones.

    PubMed

    Rey-Rodriguez, Romain; Grelier, Gwendal; Habert, Loïc; Retailleau, Pascal; Darses, Benjamin; Gillaizeau, Isabelle; Dauban, Philippe

    2017-09-01

    This article describes the reaction of ynamides with metallanitrenes generated in the presence of an iodine(III) oxidant. N-(Boc)-Ynamides are converted to oxazolones via a cyclization reaction. The reaction is mediated by a catalytic dirhodium-bound nitrene species that first behaves as a Lewis acid. The oxazolones can be converted in a one pot manner to functionalized oxazolidinones following a regio- and stereoselective oxyamination reaction with the same nitrene reagent generated in stoichiometric amounts.

  3. 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.

  4. Gas-phase enthalpies of formation and enthalpies of sublimation of amino acids based on isodesmic reaction calculations.

    PubMed

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2014-05-15

    Accurate gas-phase enthalpies of formation (ΔfH298°) of 20 common α-amino acids, seven uncommon amino acids, and three small peptides were calculated by combining G4 theory calculations with an isodesmic reaction approach. The internal consistency over a set of ΔfH298°(g) values was achieved by sequential adjustment of their values through the isodesmic reactions. Four amino acids, alanine, β-alanine, sarcosine, and glycine, with reliable internally self-consistent experimental data, were chosen as the key reference compounds. These amino acids together with about 100 compounds with reliable experimental data (their accuracy was supported by G4 calculations) were used to estimate the enthalpies of formation of remaining amino acids. All of the amino acids with the previously established enthalpies of formation were later used as the reference species in the isodesmic reactions for the other amino acids. A systematic comparison was made of 14 experimentally determined enthalpies of formation with the results of calculations. The experimental enthalpies of formation for 10 amino acids were reproduced with good accuracy, but the experimental and calculated values for 4 compounds differed by 11–21 kJ/mol. For these species, the theoretical ΔfH298°(g) values were suggested as more reliable than the experimental values. On the basis of theoretical results, the recommended values for the gas-phase enthalpies of formation were also provided for amino acids for which the experimental ΔfH298°(g) were not available. The enthalpies of sublimation were evaluated for all compounds by taking into account the literature data on the solid-phase enthalpies of formation and the ΔfH298°(g) values recommended in our work. A special attention was paid to the accurate prediction of enthalpies of formation of amino acids from the atomization reactions. The problems associated with conformational flexibility of these compounds and harmonic treatment of low frequency torsional

  5. Hydroxyl radical induced by lipid in Maillard reaction model system promotes diet-derived N(ε)-carboxymethyllysine formation.

    PubMed

    Han, Lipeng; Li, Lin; Li, Bing; Zhao, Di; Li, Yuting; Xu, Zhenbo; Liu, Guoqin

    2013-10-01

    N(ε)-carboxymethyllysine (CML) is commonly found in food, and is considered as a potential hazard to human health. However, the effect of lipids on CML formation in Maillard reaction is still not clarified. In this study, the content of diet-derived CML and its key intermediates, epsilon-fructoselysine (FL) and glyoxal (GO), is determined with high performance liquid chromatography mass spectrum (HPLC-MS) in model system containing lipid compounds. According to the results, hydroxyl radical (OH) induced by Fenton reagent can promote the three pathways of CML formation. Moreover, in the Maillard reaction system, linoleic acid (Lin), oleic acid (Ole) and glycerol trioleate (Tri) can induce more OH·, which promotes CML formation. Their level of promoting CML formation is in the order of Ole>Lin>Tri. On the contrary, glycerol (Gly) can scavenge OH·, which inhibit the CML formation. Finally, it is proved that FL content and GO content decreases with heating time in model system, while CML content increases with heating time. Thus, it is concluded that in the Maillard reaction system lipids can induce more OH·, which promotes the conversion from FL and GO to CML. Our research