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Sample records for surface reaction zone

  1. Surface modification by preparation of buffer zone in glow-discharge plasma

    International Nuclear Information System (INIS)

    Cho, D.L.

    1986-01-01

    Reactive species, energetic particles, and uv radiation in the plasma created by a glow discharge strongly interact with solid surfaces under the influence of the plasma. As a result of the strong interaction, various physical and chemical reactions, unique and advantageous for the surface modification of solid materials, occur on the solid surfaces. The surface modification is carried out through formation of a thin buffering layer on the solid surface. The preparation of a buffer zone on solid surfaces for surface modification is described. Two kinds of a buffer zone are prepared by plasma polymerization, or simultaneous sputter deposition of electrode material with plasma polymerization: a transitional buffer zone and a graded buffer zone. Important factors for preparation of the buffer zone (pre-conditioning of a substrate surface, thin-film deposition, post-treatment of the film, magnetron discharge, energy input, geometry of a substrate and a plasma) are discussed

  2. Surface-Activated Coupling Reactions Confined on a Surface.

    Science.gov (United States)

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  3. A library of prompt detonation reaction zone data

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

    Science.gov (United States)

    Wang, H; Morrison, G

    2010-06-01

    Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

  5. A field ion microscope study of the surface reaction of tungsten with n-octanol under an applied positive voltage: reaction conditions for the 'splitting' of (110) plane

    International Nuclear Information System (INIS)

    Terao, T.; Iwatsu, F.; Morikawa, H.

    1993-01-01

    Field ion microscopy is a powerful tool for the study of surface phenomena on an atomic scale, especially when they are crystal plane dependent, because the microscope shows many crystal planes of the sample tip simultaneously. Although a large number of FIM studies on vapor deposition, surface diffusion and surface reactions at a metal-gas interface have been reported, those on reactions at a metal-liquid interface are few. The authors have studied the corrosion or tungsten with aqueous solutions and found that water corroded the tungsten tips very severely to reduce the radius of curvature of the tip cap drastically. The reaction was so severe that it was not possible to trace it back to the very initial stages. They adopted, as a weaker reagent, one of the higher alcohols, n-octanol(C 8 H 17 OH), and found that it reacted with tungsten tips when an electrical pulse with a positive voltage between 5 and 10V was applied to the tip, giving very interesting field ion images in which the central (110) plane was divided into two parts located side by side across the [001] zone line. This means that some anisotropic surface reaction occurred which made a groove along the [001] zone line going through the (110) plane, usually the most stable plane chemically for bcc metals. They named this phenomenon 'splitting'. This reaction was less severe than that with water and some results on the morphology of the groove and on the reaction sequence have been reported. In the present paper more detailed reaction conditions which give rise to the splitting are described

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

    International Nuclear Information System (INIS)

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

    2010-01-01

    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.

  7. RADIATION ACCESS ZONE AND VENTILATION CONFINEMENT ZONE CRITERIA FOR THE MGR SURFACE FACILITIES

    International Nuclear Information System (INIS)

    D. A. Padula

    2000-01-01

    The objectives of this technical report are to: (1) Establish the criteria for Radiation Access Zone (RAZ) designation. (2) Establish the criteria for the Ventilation Confinement Zone (VCZ) designation. The scope will be to formulate the RAZ and VCZ zoning designation for the Monitored Geologic Repository (MGR) surface facilities and to apply the zoning designations to the current Waste Handling Building (WHB), Waste Treatment Building (WTB), and Carrier Preparation Building (CPB) configurations

  8. Investigation of (n,γ) reaction in hybrid reactor zones

    International Nuclear Information System (INIS)

    Guenay, Mehtap

    2014-01-01

    In this study, the fluids were composed with increased mole fractions of a mixture of molten salt: heavy metals 99-95 % Li 20 Sn 80 - 1-5 % SFG-Pu, 99-95 % Li 20 Sn 80 - 1-5 % SFG-PuF 4 , 99-95 % Li 20 Sn 80 - 1-5 % SFG-PuO 2 . In this study, the effect on conversion of each isotope ( 238-242 Pu) in spent fuel grade plutonium by (n,γ) reactions was investigated in liquid first wall, blanket and shield zones of the designed hybrid reactor system. Beryllium (Be) is the neutron multiplier by (n,2n) reactions. The Be zone used was 3 cm thick. 9Cr2WVT, a ferritic steel, is used as structural material. Three-dimensional nucleonic calculations were performed by using the most recent versions of the MCNPX-2.7.0 Monte Carlo code and the nuclear data library ENDF/B-VII.0.

  9. Investigation of (n,γ) reaction in hybrid reactor zones

    Energy Technology Data Exchange (ETDEWEB)

    Guenay, Mehtap [Inoenue Univ., Malatya (Turkey). Physics Dept.

    2014-12-15

    In this study, the fluids were composed with increased mole fractions of a mixture of molten salt: heavy metals 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-Pu, 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-PuF{sub 4}, 99-95 % Li{sub 20}Sn{sub 80{sup -}}1-5 % SFG-PuO{sub 2}. In this study, the effect on conversion of each isotope ({sup 238-242}Pu) in spent fuel grade plutonium by (n,γ) reactions was investigated in liquid first wall, blanket and shield zones of the designed hybrid reactor system. Beryllium (Be) is the neutron multiplier by (n,2n) reactions. The Be zone used was 3 cm thick. 9Cr2WVT, a ferritic steel, is used as structural material. Three-dimensional nucleonic calculations were performed by using the most recent versions of the MCNPX-2.7.0 Monte Carlo code and the nuclear data library ENDF/B-VII.0.

  10. Modeling of pollutant formation in fully premixing surface burners using a verified practice-oriented experimental reaction-kinetic calculation method. Final report

    International Nuclear Information System (INIS)

    Ruy, C.; Kremer, H.

    1996-01-01

    The intent of the present study was to simulate quantitatively pollutant formation in premixing surface burners and to describe qualitatively the share of the premixing flame in pollut emissions from atmospheric burners. For this purpose reaction-kinetic programmes for one-dimensional premixing flames were extended by a terms describing heat discharge through gas radiation. Furthermore, the calculation range for the flame was extended far into the secondary reaction zone. Temperature, CO, and NO x profiles were measured in the secondary reaction zone of premixing burners at standard pressure. The air-fuel ratio was calculated within the practically relevant range between 0.5 and 1.5, as was load behaviour. (DG) [de

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    Abrams , Robert H.; Loague, Keith; Kent, Douglas 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.

  13. Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flytzani-Stephanopoulos, M; Schmidt, L D

    1979-01-01

    Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

  14. On surface reactions of iron tungstate with ethane

    International Nuclear Information System (INIS)

    Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

    1980-01-01

    Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

  15. Defining the Brittle Failure Envelopes of Individual Reaction Zones Observed in CO2-Exposed Wellbore Cement.

    Science.gov (United States)

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

    2016-01-19

    To predict the behavior of the cement sheath after CO2 injection and the potential for leakage pathways, it is key to understand how the mechanical properties of the cement evolves with CO2 exposure time. We performed scratch-hardness tests on hardened samples of class G cement before and after CO2 exposure. The cement was exposed to CO2-rich fluid for one to six months at 65 °C and 8 MPa Ptotal. Detailed SEM-EDX analyses showed reaction zones similar to those previously reported in the literature: (1) an outer-reacted, porous silica-rich zone; (2) a dense, carbonated zone; and (3) a more porous, Ca-depleted inner zone. The quantitative mechanical data (brittle compressive strength and friction coefficient) obtained for each of the zones suggest that the heterogeneity of reacted cement leads to a wide range of brittle strength values in any of the reaction zones, with only a rough dependence on exposure time. However, the data can be used to guide numerical modeling efforts needed to assess the impact of reaction-induced mechanical failure of wellbore cement by coupling sensitivity analysis and mechanical predictions.

  16. Width of surface rupture zone for thrust earthquakes: implications for earthquake fault zoning

    Science.gov (United States)

    Boncio, Paolo; Liberi, Francesca; Caldarella, Martina; Nurminen, Fiia-Charlotta

    2018-01-01

    The criteria for zoning the surface fault rupture hazard (SFRH) along thrust faults are defined by analysing the characteristics of the areas of coseismic surface faulting in thrust earthquakes. Normal and strike-slip faults have been deeply studied by other authors concerning the SFRH, while thrust faults have not been studied with comparable attention. Surface faulting data were compiled for 11 well-studied historic thrust earthquakes occurred globally (5.4 ≤ M ≤ 7.9). Several different types of coseismic fault scarps characterize the analysed earthquakes, depending on the topography, fault geometry and near-surface materials (simple and hanging wall collapse scarps, pressure ridges, fold scarps and thrust or pressure ridges with bending-moment or flexural-slip fault ruptures due to large-scale folding). For all the earthquakes, the distance of distributed ruptures from the principal fault rupture (r) and the width of the rupture zone (WRZ) were compiled directly from the literature or measured systematically in GIS-georeferenced published maps. Overall, surface ruptures can occur up to large distances from the main fault ( ˜ 2150 m on the footwall and ˜ 3100 m on the hanging wall). Most of the ruptures occur on the hanging wall, preferentially in the vicinity of the principal fault trace ( > ˜ 50 % at distances guidelines). In the absence of such a very detailed study (basic SM, i.e. Level 1 SM of Italian guidelines) a width of ˜ 840 m (90 % probability from "simple thrust" database of distributed ruptures, excluding B-M, F-S and Sy fault ruptures) is suggested to be sufficiently precautionary. For more detailed SM, where the fault is carefully mapped, one must consider that the highest SFRH is concentrated in a narrow zone, ˜ 60 m in width, that should be considered as a fault avoidance zone (more than one-third of the distributed ruptures are expected to occur within this zone). The fault rupture hazard zones should be asymmetric compared to the trace

  17. Width of surface rupture zone for thrust earthquakes: implications for earthquake fault zoning

    Directory of Open Access Journals (Sweden)

    P. Boncio

    2018-01-01

    Full Text Available The criteria for zoning the surface fault rupture hazard (SFRH along thrust faults are defined by analysing the characteristics of the areas of coseismic surface faulting in thrust earthquakes. Normal and strike–slip faults have been deeply studied by other authors concerning the SFRH, while thrust faults have not been studied with comparable attention. Surface faulting data were compiled for 11 well-studied historic thrust earthquakes occurred globally (5.4 ≤ M ≤ 7.9. Several different types of coseismic fault scarps characterize the analysed earthquakes, depending on the topography, fault geometry and near-surface materials (simple and hanging wall collapse scarps, pressure ridges, fold scarps and thrust or pressure ridges with bending-moment or flexural-slip fault ruptures due to large-scale folding. For all the earthquakes, the distance of distributed ruptures from the principal fault rupture (r and the width of the rupture zone (WRZ were compiled directly from the literature or measured systematically in GIS-georeferenced published maps. Overall, surface ruptures can occur up to large distances from the main fault ( ∼ 2150 m on the footwall and  ∼  3100 m on the hanging wall. Most of the ruptures occur on the hanging wall, preferentially in the vicinity of the principal fault trace ( >   ∼  50 % at distances  <   ∼  250 m. The widest WRZ are recorded where sympathetic slip (Sy on distant faults occurs, and/or where bending-moment (B-M or flexural-slip (F-S fault ruptures, associated with large-scale folds (hundreds of metres to kilometres in wavelength, are present. A positive relation between the earthquake magnitude and the total WRZ is evident, while a clear correlation between the vertical displacement on the principal fault and the total WRZ is not found. The distribution of surface ruptures is fitted with probability density functions, in order to define a criterion to

  18. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

  19. Surface chemical reactions probed with scanning force microscopy

    NARCIS (Netherlands)

    Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

    1997-01-01

    In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

  20. Low Energy Nuclear Reaction Products at Surfaces

    Science.gov (United States)

    Nagel, David J.

    2008-03-01

    This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

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

    Science.gov (United States)

    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

  2. Specifications for surface reaction analysis apparatus

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2001-03-01

    A surface reaction analysis apparatus was installed at the JAERI soft x-ray beamline in the SPring-8 as an experimental end-station for the study of surface chemistry. The apparatus is devoted to the study concerning the influence of translational kinetic energy of incident molecules to chemical reactions on solid surfaces with gas molecules. In order to achieve the research purpose, reactive molecular scattering experiments and photoemission spectroscopic measurements using synchrotron radiation are performed in that apparatus via a supersonic molecular beam generator, an electron energy analyzer and a quadrupole mass analyzer. The detail specifications for the apparatus are described in this report. (author)

  3. Electronic dissipation processes during chemical reactions on surfaces

    CERN Document Server

    Stella, Kevin

    2012-01-01

    Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

  4. Experimental investigations of different steel resistances in the sodium-steam reaction zone

    International Nuclear Information System (INIS)

    Mazanov, A.S.; Kulpin, B.V.; Petukhov, V.P.; Ledovskikh, N.M.

    1975-01-01

    The results are stated on the experimental investigations of IX2M, IXI8HIOT, OXI2H2M and Sanikro-31 steel resistance in the sodium-steam reaction zone. A target in the form of a pipe was used in the experiments within which the excessive pressure of 95 atm. was produced with an inert gas. Steam was supplied through the nozzle to the sodium tank in which there was a movable target unit. The dependence of time-to failure and failure rate on the distance of the nozzle and target wall thickness was estimated for these steels. It was shown that the resistance of Sanikro-31 in the sodium steam reaction zone was 2.5, 3.5 and 6 times that of IXI8HIOT, OXI2H2M, IX2M steels, respectively. The failure curves were obtained on thin targets for two steels (author)

  5. Reactor Meltdown: Critical Zone Processes In Siliciclastics Unlikely To Be Directly Transferable To Carbonates

    Science.gov (United States)

    Gulley, J. D.; Cohen, M. J.; Kramer, M. G.; Martin, J. B.; Graham, W. D.

    2013-12-01

    Carbonate terrains cover 20% of Earth's ice-free land and are modified through interactions between rocks, water and biota that couple ecosystems processes to weathering reactions within the critical zone. Weathering in carbonate systems differs from the Critical Zone Reactor model developed for siliciclastic systems because reactions in siliciclastic critical zones largely consist of incongruent weathering (e.g., feldspar to secondary clay minerals) that typically occur in the soil zone within a few meters of the land surface. These incongruent reactions create regolith, which is removed by physical transport mechanisms that drive landscape denudation. In contrast, carbonate critical zones are mostly composed of homogeneous and soluble minerals, which dissolve congruently with the weathering products exported in solution, limiting regolith in the soil mantle to small amounts of insoluble residues. These reactions can extend to depths greater than 2 km below the surface. As water at the land surface drains preferentially through vertical joints and horizontal bedding planes of the carbonate critical zones, it is 'charged' with biologically-derived carbon dioxide, which decreases pH, dissolves carbonate rock, and enlarges subsurface flowpaths through feedbacks between flow and dissolution. Caves are extreme end products of this process and are key morphological features of carbonate critical zones. Caves link surface processes to the deep subsurface and serve as efficient delivery agents for oxygen, carbon and nutrients to zones within the critical zone that are deficient in all three, interrupting vertical and horizontal chemical gradients that would exist if caves were not present. We present select data from air and water-filled caves in the upper Floridan aquifer, Florida, USA, that demonstrate how caves, acting as very large preferential flow paths, alter processes in carbonate relative to siliciclastic critical zones. While caves represent an extreme end

  6. Supersonic molecular beam experiments on surface chemical reactions.

    Science.gov (United States)

    Okada, Michio

    2014-10-01

    The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Characterisation of weld zone reactions in dissimilar glass-to-aluminium pulsed picosecond laser welds

    Energy Technology Data Exchange (ETDEWEB)

    Ciuca, Octav P., E-mail: octav.ciuca@manchester.ac.uk [School of Materials, University of Manchester, Manchester, M13 9PL (United Kingdom); Carter, Richard M. [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh, EH14 4AS (United Kingdom); Prangnell, Philip B. [School of Materials, University of Manchester, Manchester, M13 9PL (United Kingdom); Hand, Duncan P. [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh, EH14 4AS (United Kingdom)

    2016-10-15

    Precision welded joints, produced between fused silica glass and aluminium by a newly-developed picosecond-pulse laser technique, have been analysed for the first time using a full range of electron microscopy methods. The welds were produced as lap joints by focusing a 1.2 μm diameter laser beam through the transparent glass top sheet, slightly below the surface of the metal bottom sheet. Despite the extremely short interaction time, extensive reaction was observed in the weld zone, which involved the formation of nanocrystalline silicon and at least two transitional alumina phases, γ- and δ-Al{sub 2}O{sub 3}. The weld formation process was found to be complex and involved: the formation of a constrained plasma cavity at the joint interface, non-linear absorption in the glass, and the creation of multiple secondary keyholes in the metal substrate by beam scattering. The joint area was found to expand outside of the main interaction volume, as the energy absorbed into the low conductivity and higher melting point silica glass sheet melted the aluminium surface across a wider contact area. The reasons for the appearance of nanocrystalline Si and transitional alumina reaction products within the welds are discussed. - Highlights: •Pulsed laser welding of dissimilar materials causes extensive chemical reactivity. •Metastable Al{sub 2}O{sub 3} phases form due to laser-induced highly-transient thermal regime. •Fused silica is reduced by Al to form nanocrystalline Si. •Mechanism of joint formation is discussed.

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

    Science.gov (United States)

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

    2006-12-01

    phases (phlogopite and amphibole) in different metasomatic zones indicate mobility of many elements, including elements such as Ta which are considered to have scarce mobility in fluids. Trace element composition of accessory minerals in the phlogopite-rich zone suggests that the trace element signature of subduction zone fluids may be fractionated in this zone. The progressive depletion in some trace elements (LREE) and enrichment in LILE and Li from the peridotite towards the gneiss suggests a strong influence of bulk composition on the trace element budget of hydrous minerals. Since the ultramafic blocks can be representative of metasomatic processes occurring at the slab-mantle interface, we can infer that metasomatic reactions between slab-derived fluids and ultramafic mantle wedge will follow a specific series of reactions, creating mineral zonation similar to those observed in this study. Our results further favour the evidence that the primary composition of subduction zone fluids is modified substantially by metasomatic reactions occurring in the mantle wedge.

  9. Fracture zones constrained by neutral surfaces in a fault-related fold: Insights from the Kelasu tectonic zone, Kuqa Depression

    Science.gov (United States)

    Sun, Shuai; Hou, Guiting; Zheng, Chunfang

    2017-11-01

    Stress variation associated with folding is one of the controlling factors in the development of tectonic fractures, however, little attention has been paid to the influence of neutral surfaces during folding on fracture distribution in a fault-related fold. In this study, we take the Cretaceous Bashijiqike Formation in the Kuqa Depression as an example and analyze the distribution of tectonic fractures in fault-related folds by core observation and logging data analysis. Three fracture zones are identified in a fault-related fold: a tensile zone, a transition zone and a compressive zone, which may be constrained by two neutral surfaces of fold. Well correlation reveals that the tensile zone and the transition zone reach the maximum thickness at the fold hinge and get thinner in the fold limbs. A 2D viscoelastic stress field model of a fault-related fold was constructed to further investigate the mechanism of fracturing. Statistical and numerical analysis reveal that the tensile zone and the transition zone become thicker with decreasing interlimb angle. Stress variation associated with folding is the first level of control over the general pattern of fracture distribution while faulting is a secondary control over the development of local fractures in a fault-related fold.

  10. Basic reactions of osteoblasts on structured material surfaces

    Directory of Open Access Journals (Sweden)

    U. Meyer

    2005-04-01

    Full Text Available In order to assess how bone substitute materials determine bone formation in vivo it is useful to understand the mechanisms of the material surface/tissue interaction on a cellular level. Artificial materials are used in two applications, as biomaterials alone or as a scaffold for osteoblasts in a tissue engineering approach. Recently, many efforts have been undertaken to improve bone regeneration by the use of structured material surfaces. In vitro studies of bone cell responses to artificial materials are the basic tool to determine these interactions. Surface properties of materials surfaces as well as biophysical constraints at the biomaterial surface are of major importance since these features will direct the cell responses. Studies on osteoblast-like cell reactivity towards materials will have to focus on the different steps of protein and cell reactions towards defined surface properties. The introduction of new techniques allows nowadays the fabrication of materials with ordered surface structures. This paper gives a review of present knowledge on the various stages of osteoblast reactions on material surfaces, focused on basic cell events under in vitro conditions. Special emphasis is given to cellular reactions towards ordered nano-sized topographies.

  11. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  12. Multifractal scaling analysis of autopoisoning reactions over a rough surface

    International Nuclear Information System (INIS)

    Chaudhari, Ajay; Yan, Ching-Cher Sanders; Lee, S.-L.

    2003-01-01

    Decay type diffusion-limited reactions (DLR) over a rough surface generated by a random deposition model were performed. To study the effect of the decay profile on the reaction probability distribution (RPD), multifractal scaling analysis has been carried out. The dynamics of these autopoisoning reactions are controlled by the two parameters in the decay function, namely, the initial sticking probability (P ini ) of every site and the decay rate (m). The smaller the decay rate, the narrower is the range of α values in the α-f(α) multifractal spectrum. The results are compared with the earlier work of DLR over a surface of diffusion-limited aggregation (DLA). We also considered here the autopoisoning reactions over a smooth surface for comparing our results, which show clearly how the roughness affects the chemical reactions. The q-τ(q) multifractal curves for the smooth surface are linear whereas those for the rough surface are nonlinear. The range of α values in the case of a rough surface is wider than that of the smooth surface

  13. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

  14. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  15. Investigation of zones with increased ground surface gamma radiation

    International Nuclear Information System (INIS)

    Butkus, D.V.; Morkunas, G.S.; Styro, B.I.

    1989-01-01

    Measurements of the increased gamma radiation zones of soils were conducted in the South-Western part of the Litvinian. The shores of lakes in the north-eastern part of the Suduva high land were investigated. the maximum values of the gamma radiation dose rates were distributed along the lake shores at a distance of 1 m from the water surface, while farther than 1.5 m from it the dose rate was close to the natural value. The increased gamma radiation intensity zones on the ground surface were found only at the northern (Lake Reketija) or the western shore (other lakes under investigation). The highest values of the gamma radiation dose 200-600 μR/h (0.5-1.5 nGy/s) were observed in the comparatively small areas (up to several square metres). The gamma radiation intensity of soil surface increased strongly moving towards the point where the maximum intensity was obsered. 10 figs

  16. Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

    International Nuclear Information System (INIS)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

    2015-01-01

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

  17. Dilution in Transition Zone between Rising Plumes and Surface Plumes

    DEFF Research Database (Denmark)

    Larsen, Torben

    2004-01-01

    The papers presents some physical experiments with the dilution of sea outfall plumes with emphasize on the transition zone where the relative fast flowing vertical plume turns to a horizontal surface plume following the slow sea surface currents. The experiments show that a considerable dilution...

  18. Reactions between monolayer Fe and Si(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hasegawa, M; Kobayashi, N; Hayashi, N [Electrotechnical Lab., Tsukuba, Ibaraki (Japan)

    1997-03-01

    Reactions between 1.5 monolayer(ML) Fe deposited on Si(001)-2x1 and -dihydride surfaces were studied in situ by reflection high-energy electron diffraction and time-of-flight ion scattering spectrometry with the use of 25 keV H ions. The reactions between Fe and Si which were successively deposited on Si(001)-dihydride surface were also studied. After the room temperature deposition Fe reacted with Si(001)-2x1 substrate resulting in the formation of polycrystalline Fe5Si3. By annealing to 560-650degC composite heteroepitaxial layer of both type A and type B {beta}-FeSi2 was formed. On the dihydride surface polycrystalline Fe was observed after 1.5ML Fe deposition at room temperature, and reaction between Fe and Si(001)-dihydride surface is not likely at room temperature. We observed 3D rough surface when we deposited only Fe layer on the dihydride surface and annealed above 700degC. The hydrogen termination of Si(001) surface prevents the deposited Fe from diffusing into the substrate below 500degC, however the annealing above 710degC leads to the diffusion. We obtained 2D ordered surface, which showed 3x3 RHEED pattern as referenced to the primitive unreconstructed Si(001) surface net, when we deposited 2.5ML Fe and 5.8ML Si successively onto Si(001)-dihydride surface and annealed to 470degC. (author)

  19. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Science.gov (United States)

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  20. Local stresses, dyke arrest and surface deformation in volcanic edificesand rift zones

    Directory of Open Access Journals (Sweden)

    L. S. Brenner

    2004-06-01

    Full Text Available Field studies indicate that nearly all eruptions in volcanic edifices and rift zones are supplied with magma through fractures (dykes that are opened by magmatic overpressure. While (inferred dyke injections are frequent during unrest periods, volcanic eruptions are, in comparison, infrequent, suggesting that most dykes become arrested at certain depths in the crust, in agreement with field studies. The frequency of dyke arrest can be partly explained by the numerical models presented here which indicate that volcanic edifices and rift zones consisting of rocks of contrasting mechanical properties, such as soft pyroclastic layers and stiff lava flows, commonly develop local stress fields that encourage dyke arrest. During unrest, surface deformation studies are routinely used to infer the geometries of arrested dykes, and some models (using homogeneous, isotropic half-spaces infer large grabens to be induced by such dykes. Our results, however, show that the dyke-tip tensile stresses are normally much greater than the induced surface stresses, making it difficult to explain how a dyke can induce surface stresses in excess of the tensile (or shear strength while the same strength is not exceeded at the (arrested dyke tip. Also, arrested dyke tips in eroded or active rift zones are normally not associated with dyke-induced grabens or normal faults, and some dykes arrested within a few metres of the surface do not generate faults or grabens. The numerical models show that abrupt changes in Young's moduli(stiffnesses, layers with relatively high dyke-normal compressive stresses (stress barriers, and weak horizontal contacts may make the dyke-induced surface tensile stresses too small for significant fault or graben formation to occur in rift zones or volcanic edifices. Also, these small surface stresses may have no simple relation to the dyke geometry or the depth to its tip. Thus, for a layered crust with weak contacts, straightforward

  1. Pd-catalyzed coupling reaction on the organic monolayer: Sonogashira reaction on the silicon (1 1 1) surfaces

    International Nuclear Information System (INIS)

    Qu Mengnan; Zhang Yuan; He Jinmei; Cao Xiaoping; Zhang Junyan

    2008-01-01

    Iodophenyl-terminated organic monolayers were prepared by thermally induced hydrosilylation on hydrogen-terminated silicon (1 1 1) surfaces. The films were characterized by ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy (XPS). To modify the surface chemistry and the structure of the monolayers, the Sonogashira coupling reaction was performed on the as-prepared monolayers. The iodophenyl groups on the film surfaces reacted with 1-ethynyl-4-fluorobenzene or the 1-chloro-4-ethynylbenzene under the standard Sonogashira reaction conditions for attaching conjugated molecules via the formation of C-C bonds. It is expected that this surface coupling reaction will present a new method to modify the surface chemistry and the structure of monolayers

  2. TECHNICAL BASIS FOR EVALUATING SURFACE BARRIERS TO PROTECT GROUNDWATER FROM DEEP VADOSE ZONE CONTAMINATION

    International Nuclear Information System (INIS)

    Fayer, J.M.; Freedman, V.L.; Ward, A.L.; Chronister, G.B.

    2010-01-01

    The U.S. DOE and its predecessors released nearly 2 trillion liters (450 billion gallons) of contaminated liquid into the vadose zone at the Hanford Site. Some of the contaminants currently reside in the deeper parts of the vadose zone where they are much less accessible to characterization, monitoring, and typical remediation activities. The DOE Richland Operations Office (DOE-RL) prepared a treatability test plan in 2008 to examine remediation options for addressing contaminants in the deep vadose zone; one of the technologies identified was surface barriers (also known as engineered barriers, covers, and caps). In the typical configuration, the contaminants are located relatively close to the surface, generally within 15 m, and thus they are close to the base of the surface barrier. The proximity of the surface barrier under these conditions yielded few concerns about the effectiveness of the barrier at depth, particularly for cases in which the contaminants were in a lined facility. At Hanford, however, some unlined sites have contaminants located well below depths of 15 m. The issue raised about these sites is the degree of effectiveness of a surface barrier in isolating contaminants in the deep vadose zone. Previous studies by Hanford Site and PNNL researchers suggest that surface barriers have the potential to provide a significant degree of isolation of deep vadose zone contaminants. The studies show that the actual degree of isolation is site-specific and depends on many factors, including recharge rates, barrier size, depth of contaminants, geohydrologic properties ofthe sediments, and the geochemical interactions between the contaminants and the sediments. After the DOE-RL treatability test plan was published, Pacific Northwest National Laboratory was contracted to review the information available to support surface barrier evaluation for the deep vadose zone, identify gaps in the information and outcomes necessary to fill the data gaps, and outline

  3. Width of the Surface Rupture Zone for Thrust Earthquakes and Implications for Earthquake Fault Zoning: Chi-Chi 1999 and Wenchuan 2008 Earthquakes

    Science.gov (United States)

    Boncio, P.; Caldarella, M.

    2016-12-01

    We analyze the zones of coseismic surface faulting along thrust faults, whit the aim of defining the most appropriate criteria for zoning the Surface Fault Rupture Hazard (SFRH) along thrust faults. Normal and strike-slip faults were deeply studied in the past, while thrust faults were not studied with comparable attention. We analyze the 1999 Chi-Chi, Taiwan (Mw 7.6) and 2008 Wenchuan, China (Mw 7.9) earthquakes. Several different types of coseismic fault scarps characterize the two earthquakes, depending on the topography, fault geometry and near-surface materials. For both the earthquakes, we collected from the literature, or measured in GIS-georeferenced published maps, data about the Width of the coseismic Rupture Zone (WRZ). The frequency distribution of WRZ compared to the trace of the main fault shows that the surface ruptures occur mainly on and near the main fault. Ruptures located away from the main fault occur mainly in the hanging wall. Where structural complexities are present (e.g., sharp bends, step-overs), WRZ is wider then for simple fault traces. We also fitted the distribution of the WRZ dataset with probability density functions, in order to define a criterion to remove outliers (e.g., by selecting 90% or 95% probability) and define the zone where the probability of SFRH is the highest. This might help in sizing the zones of SFRH during seismic microzonation (SM) mapping. In order to shape zones of SFRH, a very detailed earthquake geologic study of the fault is necessary. In the absence of such a very detailed study, during basic (First level) SM mapping, a width of 350-400 m seems to be recommended (95% of probability). If the fault is carefully mapped (higher level SM), one must consider that the highest SFRH is concentrated in a narrow zone, 50 m-wide, that should be considered as a "fault-avoidance (or setback) zone". These fault zones should be asymmetric. The ratio of footwall to hanging wall (FW:HW) calculated here ranges from 1:5 to 1:3.

  4. Monitoring the Vadose Zone Moisture Regime Below a Surface Barrier

    Science.gov (United States)

    Zhang, Z. F.; Strickland, C. E.; Field, J. G.

    2009-12-01

    A 6000 m2 interim surface barrier has been constructed over a portion of the T Tank Farm in the Depart of Energy’s Hanford site. The purpose of using a surface barrier was to reduce or eliminate the infiltration of meteoric precipitation into the contaminated soil zone due to past leaks from Tank T-106 and hence to reduce the rate of movement of the plume. As part of the demonstration effort, vadose zone moisture is being monitored to assess the effectiveness of the barrier on the reduction of soil moisture flow. A vadose zone monitoring system was installed to measure soil water conditions at four horizontal locations (i.e., instrument Nests A, B, C, and D) outside, near the edge of, and beneath the barrier. Each instrument nest consists of a capacitance probe with multiple sensors, multiple heat-dissipation units, and a neutron probe access tube used to measure soil-water content and soil-water pressure. Nest A serves as a control by providing subsurface conditions outside the influence of the surface barrier. Nest B provides subsurface measurements to assess barrier edge effects. Nests C and D are used to assess the impact of the surface barrier on soil-moisture conditions beneath it. Monitoring began in September 2006 and continues to the present. To date, the monitoring system has provided high-quality data. Results show that the soil beneath the barrier has been draining from the shallower depth. The lack of climate-caused seasonal variation of soil water condition beneath the barrier indicates that the surface barrier has minimized water exchange between the soil and the atmosphere.

  5. Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

    Science.gov (United States)

    Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

    2016-09-01

    It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

  6. Surface Wave Focusing and Acoustic Communications in the Surf Zone

    National Research Council Canada - National Science Library

    Preisig, James

    2004-01-01

    The forward scattering of acoustic signals off of shoaling surface gravity waves in the surf zone results in a time-varying channel impulse response that is characterized by intense, rapidly fluctuating arrivals...

  7. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  8. Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

    2015-10-15

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

  9. Zone separator for multiple zone vessels

    Science.gov (United States)

    Jones, John B.

    1983-02-01

    A solids-gas contact vessel, having two vertically disposed distinct reaction zones, includes a dynamic seal passing solids from an upper to a lower zone and maintaining a gas seal against the transfer of the separate treating gases from one zone to the other, and including a stream of sealing fluid at the seal.

  10. Hydrodynamic Characterization of a Surface Storage Zone in a Natural Stream

    Science.gov (United States)

    Sandoval Ulloa, J. C.; Escauriaza, C. R.; Mignot, E.; Mao, L.

    2015-12-01

    Flow developed in surface storage zones in rivers is very important for many physical and biogeochemical processes. These regions are characterized by low velocities compared to the flow in the main channel and long residence times that favor the deposition of contaminants, nutrient uptake and interactions with reactive sediments. The dynamics of the turbulent flows in these zones is very complex, typically characterized by a shear layer that induces a recirculating area, with multiple large-scale coherent structures of different temporal and spatial scales. In this work we present the methodology and analysis of measurements in a natural surface storage zone. We report detailed information of a field campaign carried out in the Lluta River, located in northern Chile in the high altitude Andean environment known as the Altiplano (~4,000 masl). The area of study has great interest for the river ecosystem, since the water has high concentration levels of arsenic and other metals. The Lluta River is also a water source for many agricultural communities and urban centers located in the lower parts of the watershed. Field information obtained was: detailed topography, 3D velocity components in several points, and sediment arsenic concentration in the main channel and in the recirculating region of the natural surface storage zone. Topography was obtained through DGPS and digital image processing. The 3D velocity field was measured with an acoustic Doppler velocimeter (ADV) and surface velocity data was obtained through the LSPIV technique. Arsenic concentration was obtained by sediment sampling analysis. With this data we analyze the flow topology and characteristics features of the velocity, which constitute the controlling mechanisms of contaminant transport in the field. In addition, we contrast with preliminary results of a three-dimensional (3D) numerical simulation, to determine the influence of different parameters on the transport and mixing processes in natural

  11. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  12. Chemical reaction on solid surface observed through isotope tracer technique

    International Nuclear Information System (INIS)

    Tanaka, Ken-ichi

    1983-01-01

    In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

  13. Laser surface pretreatment of 100Cr6 bearing steel – Hardening effects and white etching zones

    International Nuclear Information System (INIS)

    Buling, Anna; Sändker, Hendrik; Stollenwerk, Jochen; Krupp, Ulrich; Hamann-Steinmeier, Angela

    2016-01-01

    Highlights: • Laser surface pretreatment of the bearing steel 100Cr6 is performed. • Microstructural changes of the surface are examined by light microscopy and SEM. • Topographical changes are observed using white light interferometry. • Micro-hardness testing show the existence of very hard white etching zones (WEZ). • WEZ are attributed to near-surface reaustenitization and rapid quenching. • Dark etching zones (DEZ) are found at the laser path edges after laser pretreatment. - Abstract: In order to achieve a surface pretreatment of the bearing steel 100Cr6 (1–1.5 wt.% Cr) a laser-based process was used. The obtained modification may result in an optimization of the adhesive properties of the surface with respect to an anticorrosion polymer coating on the basis of PEEK (poly-ether-ether-ketone), which is applied on the steel surface by a laser melting technique. This work deals with the influence of the laser-based pretreatment regarding the surface microstructure and the micro-hardness of the steel, which has been examined by scanning electron microscopy (SEM), light microscopy and automated micro-hardness testing. The most suitable parameter set for the laser-based pretreatment leads to the formation of very hard white etching zones (WEZ) with a thickness of 23 μm, whereas this pretreatment also induces topographical changes. The occurrence of the white etching zones is attributed to near-surface re-austenitization and rapid quenching. Moreover, dark etching zones (DEZ) with a thickness of 32 μm are found at the laser path edges as well as underneath the white etching zones (WEZ). In these areas, the hardness is decreased due to the formation of oxides as a consequence of re-tempering.

  14. Laser surface pretreatment of 100Cr6 bearing steel – Hardening effects and white etching zones

    Energy Technology Data Exchange (ETDEWEB)

    Buling, Anna, E-mail: a.buling@hs-osnabrueck.de [Faculty of Engineering and Computer Science, University of Applied Sciences, 49009 Osnabrück (Germany); Sändker, Hendrik; Stollenwerk, Jochen [Fraunhofer Institute for Laser Technology ILT, Steinbachstrasse 15, 52074 Aachen (Germany); Krupp, Ulrich; Hamann-Steinmeier, Angela [Faculty of Engineering and Computer Science, University of Applied Sciences, 49009 Osnabrück (Germany)

    2016-08-15

    Highlights: • Laser surface pretreatment of the bearing steel 100Cr6 is performed. • Microstructural changes of the surface are examined by light microscopy and SEM. • Topographical changes are observed using white light interferometry. • Micro-hardness testing show the existence of very hard white etching zones (WEZ). • WEZ are attributed to near-surface reaustenitization and rapid quenching. • Dark etching zones (DEZ) are found at the laser path edges after laser pretreatment. - Abstract: In order to achieve a surface pretreatment of the bearing steel 100Cr6 (1–1.5 wt.% Cr) a laser-based process was used. The obtained modification may result in an optimization of the adhesive properties of the surface with respect to an anticorrosion polymer coating on the basis of PEEK (poly-ether-ether-ketone), which is applied on the steel surface by a laser melting technique. This work deals with the influence of the laser-based pretreatment regarding the surface microstructure and the micro-hardness of the steel, which has been examined by scanning electron microscopy (SEM), light microscopy and automated micro-hardness testing. The most suitable parameter set for the laser-based pretreatment leads to the formation of very hard white etching zones (WEZ) with a thickness of 23 μm, whereas this pretreatment also induces topographical changes. The occurrence of the white etching zones is attributed to near-surface re-austenitization and rapid quenching. Moreover, dark etching zones (DEZ) with a thickness of 32 μm are found at the laser path edges as well as underneath the white etching zones (WEZ). In these areas, the hardness is decreased due to the formation of oxides as a consequence of re-tempering.

  15. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

    2013-05-15

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  16. Capability of LEP-type surfaces to describe noncollinear reactions 2 - Polyatomic systems

    CERN Document Server

    Espinosa-Garcia, Joaquin

    2001-01-01

    In this second article of the series, the popular LEP-type surface for collinear reaction paths and a "bent" surface, which involves a saddle point geometry with a nonlinear central angle, were used to examine the capacity of LEP-type surfaces to describe the kinetics and dynamics of noncollinear reaction paths in polyatomic systems. Analyzing the geometries, vibrational frequencies, curvature along the reaction path (to estimate the tunneling effect and the reaction coordinate-bound modes coupling), and the variational transition- state theory thermal rate constants for the NH//3 + O(**3P) reaction, we found that the "collinear" LEP-type and the "bent" surfaces for this polyatomic system show similar behavior, thus allowing a considerable saving in time and computational effort. This agreement is especially encouraging for this polyatomic system because in the Cs symmetry the reaction proceeds via two electronic states of symmetries **3A prime and **3A double prime , which had to be independently calibrated....

  17. Spatial distributions of biogeochemical reactions in freshwater-saltwater mixing zones of sandy beach aquifers

    Science.gov (United States)

    Kim, K. H.; Michael, H. A.; Ullman, W. J.; Cai, W. J.

    2017-12-01

    Beach aquifers host biogeochemically dynamic mixing zones between fresh and saline groundwaters of contrasting origins, histories, and compositions. Seawater, driven up the beachface by waves and tides, infiltrates into the sand and meets the seaward-discharging fresh groundwater, creating and maintaining a highly reactive intertidal circulation cell well-defined by salinity. Seawater supplies oxygen and reactive carbon to the circulation cell, supporting biogeochemical reactions within the cell that transform and attenuate dissolved nutrient fluxes from terrestrial sources. We investigated the spatial distribution of chemical reaction zones within the intertidal circulation cell at Cape Shores, Lewes, Delaware. Porewater samples were collected from multi-level wells along a beach-perpendicular transect. Samples were analyzed for particulate carbon and reactive solutes, and incubated to obtain rates of oxic respiration and denitrification. High rates of oxic respiration were observed higher on the beach, in the landward freshwater-saline water mixing zone, where dissolved oxygen availability was high. Denitrification was dominant in lower areas of the beach, below the intertidal discharge point. High respiration rates did not correlate with particulate carbon concentrations entrained within porewater, suggesting that dissolved organic carbon or immobile particulate carbon trapped within the sediment can contribute to and alter bulk reactivity. A better understanding of the sources and sinks of carbon within the beach will improve our ability to predict nutrient fluxes to estuaries and oceans, aiding the management of coastal environments and ecosystems.

  18. Self-activated, self-limiting reactions on Si surfaces

    DEFF Research Database (Denmark)

    Morgen, Per; Hvam, Jeanette; Bahari, Ali

    The direct thermally activated reactions of oxygen and ammonia with Si surfaces in furnaces have been used for a very long time in the semiconductor industry for the growth of thick oxides and nitride layers respectively. The oxidation mechanism was described in the Deal-Grove model as a diffusion...... mechanism for the direct growth of ultrathin films (0-3 nm) of oxides and nitrides under ultrahigh vacuum conditions. Neutral oxygen and a microwave excited nitrogen plasma interact directly with Si surfaces kept at different temperatures during the reaction. The gas pressures are around 10-6 Torr...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...

  19. Theory of the reaction dynamics of small molecules on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

    2016-09-09

    The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H2, H2O and CH4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

  20. A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

    Science.gov (United States)

    Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

    2012-12-21

    Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

  1. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

    2003-02-21

    The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  2. Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

    International Nuclear Information System (INIS)

    Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

    2012-01-01

    The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

  3. Reaction and Aggregation Dynamics of Cell Surface Receptors

    Science.gov (United States)

    Wang, Michelle Dong

    This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

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

    Science.gov (United States)

    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.

  5. Study on reduction reactions of neptunium(V) on magnetite surface

    International Nuclear Information System (INIS)

    Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

    2004-01-01

    Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

  6. Definition of a critical confining zone using surface geophysical methods

    International Nuclear Information System (INIS)

    Eddy-Dilek, C.A.; Hoekstra, P.; Harthill, N.; Blohm, M.; Phillips, D.R.

    1996-01-01

    Definition of the hydrogeologic framework in layered sediments of fluvial and deltaic origin is a difficult challenge for environmental characterization and remediation programs due to the lithologic and stratigraphic heterogeneities inherent in these settings. These heterogeneties often control contaminant transport and the effectiveness of remediation alternatives, Surface geophysical surveys can be cost-effective methods for characterization, but individual methods have inherent limitations in resolution and sensitivity. A synergistic approach, utilizing two geophysical survey methods was applied, to define and examine the nature and extent of a deep confining zone of regulatory importance, the Crouch Branch Confining Unit, in Coastal Plain sediments at the Savannah River Site. TDEM accurately maps the overall conductance (product of thickness and electrical conductivity) of a confining zone clay facies; from variation in conductance, changes in lithology of the conforming zone can be inferred. Shear wave seismic reflection surveys map the depth to the clay layers, and the clay layer thickness, but provides little information on the lithologic nature of the confining zone. Integrated interpretation of the combined data set (including all available borehole logs) allows for delineation of the lateral and vertical extent of clay-dominated zones, sand-dominated zones, key stratigraphic horizons, and erosional features associated with unconformities. This approach has resulted in the collection of critical information that will be used to optimize remedial system design, representing a significant cost savings to environmental restoration programs at the Savannah River Site

  7. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  8. Imbalance in Groundwater-Surface Water Interactions and its Relationship to the Coastal Zone Hazards

    Science.gov (United States)

    Kontar, Y. A.; Ozorovich, Y. R.; Salokhiddinov, A. T.

    2011-12-01

    We report here some efforts and results in studying the imbalance in groundwater-surface water interactions and processes of groundwater-surface water interactions and groundwater flooding creating hazards in the coastal zones. Hazards, hydrological and geophysical risk analysis related to imbalance in groundwater-surface water interactions and groundwater flooding have been to a large extent under-emphasized for coastal zone applications either due to economical limitations or underestimation of significance of imbalance in groundwater-surface water interactions. This is particularly true for tsunamis creating salt water intrusion to coastal aquifers, even though most tsunami hazard assessments have in the past relied on scenario or deterministic type models, and to increasing mineralization of potable water because of intensive water diversions and also the abundance of highly toxic pollutants (mainly pesticides) in water, air and food, which contribute to the deterioration of the coastal population's health. In the wake of pressing environmental and economic issues, it is of prime importance for the scientific community to shed light onto the great efforts by hydrologists and geophysicists to quantify conceptual uncertainties and to provide quality assurances of potential coastal zone hazard evaluation and prediction under conditions of imbalance in groundwater-surface water interactions. This paper proposes consideration of two case studies which are important and significant for future understanding of a concept of imbalance in groundwater-surface water interactions and development and essential for feasibility studies of hazards in the coastal zone. The territory of the Aral Sea Region in Central Asia is known as an ecological disaster coastal zone. It is now obvious that, in order to provide reasonable living conditions to the coastal zone population, it is first of all necessary to drastically improve the quality of the water dedicated to human needs. Due

  9. Theoretical Study of Sodium-Water Surface Reaction Mechanism

    Science.gov (United States)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

  10. Theoretical study of sodium-water surface reaction mechanism

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    2012-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  11. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

    2017-02-01

    Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  12. INDICATION OF INSENSITIVITY OF PLANETARY WEATHERING BEHAVIOR AND HABITABLE ZONE TO SURFACE LAND FRACTION

    International Nuclear Information System (INIS)

    Abbot, Dorian S.; Ciesla, Fred J.; Cowan, Nicolas B.

    2012-01-01

    It is likely that unambiguous habitable zone terrestrial planets of unknown water content will soon be discovered. Water content helps determine surface land fraction, which influences planetary weathering behavior. This is important because the silicate-weathering feedback determines the width of the habitable zone in space and time. Here a low-order model of weathering and climate, useful for gaining qualitative understanding, is developed to examine climate evolution for planets of various land-ocean fractions. It is pointed out that, if seafloor weathering does not depend directly on surface temperature, there can be no weathering-climate feedback on a waterworld. This would dramatically narrow the habitable zone of a waterworld. Results from our model indicate that weathering behavior does not depend strongly on land fraction for partially ocean-covered planets. This is powerful because it suggests that previous habitable zone theory is robust to changes in land fraction, as long as there is some land. Finally, a mechanism is proposed for a waterworld to prevent complete water loss during a moist greenhouse through rapid weathering of exposed continents. This process is named a 'waterworld self-arrest', and it implies that waterworlds can go through a moist greenhouse stage and end up as planets like Earth with partial ocean coverage. This work stresses the importance of surface and geologic effects, in addition to the usual incident stellar flux, for habitability.

  13. INDICATION OF INSENSITIVITY OF PLANETARY WEATHERING BEHAVIOR AND HABITABLE ZONE TO SURFACE LAND FRACTION

    Energy Technology Data Exchange (ETDEWEB)

    Abbot, Dorian S.; Ciesla, Fred J. [Department of the Geophysical Sciences, University of Chicago, 5734 South Ellis Avenue, Chicago, IL 60637 (United States); Cowan, Nicolas B., E-mail: abbot@uchicago.edu [Center for Interdisciplinary Exploration and Research in Astrophysics (CIERA) and Department of Physics and Astronomy, Northwestern University, 2131 Tech Drive, Evanston, IL 60208 (United States)

    2012-09-10

    It is likely that unambiguous habitable zone terrestrial planets of unknown water content will soon be discovered. Water content helps determine surface land fraction, which influences planetary weathering behavior. This is important because the silicate-weathering feedback determines the width of the habitable zone in space and time. Here a low-order model of weathering and climate, useful for gaining qualitative understanding, is developed to examine climate evolution for planets of various land-ocean fractions. It is pointed out that, if seafloor weathering does not depend directly on surface temperature, there can be no weathering-climate feedback on a waterworld. This would dramatically narrow the habitable zone of a waterworld. Results from our model indicate that weathering behavior does not depend strongly on land fraction for partially ocean-covered planets. This is powerful because it suggests that previous habitable zone theory is robust to changes in land fraction, as long as there is some land. Finally, a mechanism is proposed for a waterworld to prevent complete water loss during a moist greenhouse through rapid weathering of exposed continents. This process is named a 'waterworld self-arrest', and it implies that waterworlds can go through a moist greenhouse stage and end up as planets like Earth with partial ocean coverage. This work stresses the importance of surface and geologic effects, in addition to the usual incident stellar flux, for habitability.

  14. Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

    Science.gov (United States)

    Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

    We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

  15. Surface deformation in volcanic rift zones

    Science.gov (United States)

    Pollard, D.D.; Delaney, P.T.; Duffield, W.A.; Endo, E.T.; Okamura, A.T.

    1983-01-01

    The principal conduits for magma transport within rift zones of basaltic volcanoes are steeply dipping dikes, some of which feed fissure eruptions. Elastic displacements accompanying a single dike emplacement elevate the flanks of the rift relative to a central depression. Concomitant normal faulting may transform the depression into a graben thus accentuating the topographic features of the rift. If eruption occurs the characteristic ridge-trough-ridge displacement profile changes to a single ridge, centered at the fissure, and the erupted lava alters the local topography. A well-developed rift zone owes its structure and topography to the integrated effects of many magmatic rifting events. To investigate this process we compute the elastic displacements and stresses in a homogeneous, two-dimensional half-space driven by a pressurized crack that may breach the surface. A derivative graphical method permits one to estimate the three geometric parameters of the dike (height, inclination, and depth-to-center) and the mechanical parameter (driving pressure/rock stiffness) from a smoothly varying displacement profile. Direct comparison of measured and theoretical profiles may be used to estimate these parameters even if inelastic deformation, notably normal faulting, creates discontinuities in the profile. Geological structures (open cracks, normal faults, buckles, and thrust faults) form because of stresses induced by dike emplacement and fissure eruption. Theoretical stress states associated with dilation of a pressurized crack are used to interpret the distribution and orientation of these structures and their role in rift formation. ?? 1983.

  16. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

    2016-06-15

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  17. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    International Nuclear Information System (INIS)

    Nguyen, Luan; Tao, Franklin

    2016-01-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  18. Surface reactivity and layer analysis of chemisorbed reaction films in ...

    Indian Academy of Sciences (India)

    Administrator

    Surface reactivity and layer analysis of chemisorbed reaction films in ... in the nitrogen environment. Keywords. Surface reactivity ... sium (Na–K) compounds in the coating or core of the ..... Barkshire I R, Pruton M and Smith G C 1995 Appl. Sur.

  19. Microstructure of Reaction Zone Formed During Diffusion Bonding of TiAl with Ni/Al Multilayer

    Science.gov (United States)

    Simões, Sónia; Viana, Filomena; Koçak, Mustafa; Ramos, A. Sofia; Vieira, M. Teresa; Vieira, Manuel F.

    2012-05-01

    In this article, the characterization of the interfacial structure of diffusion bonding a TiAl alloy is presented. The joining surfaces were modified by Ni/Al reactive multilayer deposition as an alternative approach to conventional diffusion bonding. TiAl substrates were coated with alternated Ni and Al nanolayers. The nanolayers were deposited by dc magnetron sputtering with 14 nm of period (bilayer thickness). Joining experiments were performed at 900 °C for 30 and 60 min with a pressure of 5 MPa. Cross sections of the joints were prepared for characterization of their interfaces by scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), high resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). Several intermetallic compounds form at the interface, assuring the bonding of the TiAl. The interface can be divided into three distinct zones: zone 1 exhibits elongated nanograins, very small equiaxed grains are observed in zone 2, while zone 3 has larger equiaxed grains. EBSD analysis reveals that zone 1 corresponds to the intermetallic Al2NiTi and AlNiTi, and zones 2 and 3 to NiAl.

  20. Surface Defect Passivation and Reaction of c-Si in H2S.

    Science.gov (United States)

    Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

    2017-12-26

    A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

  1. Structure of the Cascadia Subduction Zone Imaged Using Surface Wave Tomography

    Science.gov (United States)

    Schaeffer, A. J.; Audet, P.

    2017-12-01

    Studies of the complete structure of the Cascadia subduction zone from the ridge to the arc have historically been limited by the lack of offshore ocean bottom seismograph (OBS) infrastructure. On land, numerous dense seismic deployments have illuminated detailed structures and dynamics associated with the interaction between the subducting oceanic plate and the overriding continental plate, including cycling of fluids, serpentinization of the overlying forearc mantle wedge, and the location of the upper surface of the Juan de Fuca plate as it subducts beneath the Pacific Northwest. In the last half-decade, the Cascadia Initiative (CI), along with Neptune (ONC) and several other OBS initiatives, have instrumented both the continental shelf and abyssal plains off shore of the Cascadia subduction zone, facilitating the construction of a complete picture of the subduction zone from ridge to trench and volcanic arc. In this study, we present a preliminary azimuthally anisotropic surface-wave phase-velocity based model of the complete system, capturing both the young, unaltered Juan de Fuca plate from the ridge, to its alteration as it enters the subduction zone, in addition to the overlying continent. This model is constructed from a combination of ambient noise cross-correlations and teleseismic two station interferometry, and combines together concurrently running offshore OBS and onshore stations. We furthermore perform a number of representative 1D depth inversions for shear velocity to categorize the pristine oceanic, subducted oceanic, and continental crust and lithospheric structure. In the future the dispersion dataset will be jointly inverted with receiver functions to constrain a 3D shear-velocity model of the complete region.

  2. 30 CFR 761.15 - Procedures for waiving the prohibition on surface coal mining operations within the buffer zone...

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Procedures for waiving the prohibition on surface coal mining operations within the buffer zone of an occupied dwelling. 761.15 Section 761.15... surface coal mining operations within the buffer zone of an occupied dwelling. (a) This section does not...

  3. Oklo natural reactor. Study of uranium and rare earths migration on a core drilled through a reaction zone. Application to determination of the date of the nuclear reaction by measurement of fission products

    International Nuclear Information System (INIS)

    Ruffenach, J.C.

    1977-01-01

    Isotopic and chemical analysis of uranium and five rare earths: neodymium, samarium, europium, gadolinium and dysprosium were effected on fourteen samples taken in the same core drilled through a reaction zone of the Oklo uranium deposit. This study points out the general stability of uranium and fission rare earths; spatial distributions of these elements are quite analogous. Migrations have affected about 5% only of fission neodymium in the core of the reaction zone; corresponding values for samarium and gadolinium are slightly higher. These migration phenomena have carried rare earths to no more than 80 cm out of the core. By study of the europium it is shown that nuclear reactions have stayed in the ground since the time of reactions. On the other hand it is shown by analysis of the dysprosium that rare earths have not undergone an important movement. This study allow also the datation of nuclear reactions from the measurement of the quantity of fission neodymium produced. A value of 1.98x10 9 years is obtained slightly higher than the value obtained by geochronology [fr

  4. Molecular-dynamics analysis of mobile helium cluster reactions near surfaces of plasma-exposed tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Lin; Maroudas, Dimitrios, E-mail: maroudas@ecs.umass.edu [Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003-9303 (United States); Hammond, Karl D. [Department of Chemical Engineering, University of Missouri, Columbia, Missouri 65211 (United States); Wirth, Brian D. [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States)

    2015-10-28

    We report the results of a systematic atomic-scale analysis of the reactions of small mobile helium clusters (He{sub n}, 4 ≤ n ≤ 7) near low-Miller-index tungsten (W) surfaces, aiming at a fundamental understanding of the near-surface dynamics of helium-carrying species in plasma-exposed tungsten. These small mobile helium clusters are attracted to the surface and migrate to the surface by Fickian diffusion and drift due to the thermodynamic driving force for surface segregation. As the clusters migrate toward the surface, trap mutation (TM) and cluster dissociation reactions are activated at rates higher than in the bulk. TM produces W adatoms and immobile complexes of helium clusters surrounding W vacancies located within the lattice planes at a short distance from the surface. These reactions are identified and characterized in detail based on the analysis of a large number of molecular-dynamics trajectories for each such mobile cluster near W(100), W(110), and W(111) surfaces. TM is found to be the dominant cluster reaction for all cluster and surface combinations, except for the He{sub 4} and He{sub 5} clusters near W(100) where cluster partial dissociation following TM dominates. We find that there exists a critical cluster size, n = 4 near W(100) and W(111) and n = 5 near W(110), beyond which the formation of multiple W adatoms and vacancies in the TM reactions is observed. The identified cluster reactions are responsible for important structural, morphological, and compositional features in the plasma-exposed tungsten, including surface adatom populations, near-surface immobile helium-vacancy complexes, and retained helium content, which are expected to influence the amount of hydrogen re-cycling and tritium retention in fusion tokamaks.

  5. Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

    Science.gov (United States)

    Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

    2009-06-03

    Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

  6. Reactions of BBr(n)(+) (n = 0--2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion--surface scattering.

    Science.gov (United States)

    Wade, N; Shen, J; Koskinen, J; Cooks, R G

    2001-07-01

    Ion-surface reactions involving BBr(n)(+) (n = 0--2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B(+) ion yield BF(2)(+) at threshold energy with the simpler product ion BF(+)* appearing at higher collision energies and remaining of lower abundance than BF(2)(+) at all energies examined. In addition, the reactively sputtered ion CF(+) accompanies the formation of BF(2)(+) at low collision energies. These results stand in contrast with previous data on the ion-surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF(2)(+) being the thermodynamically favored product. The fact that the abundance of BF(2)(+) is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum--surface interface, one which involves interaction of the B(+) ion simultaneously with two fluorine atoms. By contrast with the reaction of B(+), the odd-electron species BBr(+)* reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF(+). Corresponding gas-phase ion--molecule experiments involving B(+) and BBr(+)* with C(6)F(14) also yield the products BF(+)* and BF(2)(+), but only in extremely low abundances and with no preference for double fluorine abstraction. Ion--surface reactions were also investigated for BBr(n)(+) (n = 0-2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B(+) ion and dissociative reactions of BBr(+)* result in the formation of BH(2)(+), while the thermodynamically less favorable product BH(+)* is not observed. Collisions of BBr(2)(+) with the H-SAM surface yield the dissociative ion-surface reaction products, BBrH(+) and BBrCH(3

  7. Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

    Science.gov (United States)

    Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

    2003-10-01

    The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

  8. Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

    Science.gov (United States)

    Hodgson, Murray; Wareing, Andrew

    2008-01-01

    A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.

  9. DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

    Energy Technology Data Exchange (ETDEWEB)

    Cyburt, R. H.; Keek, L.; Schatz, H. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Amthor, A. M. [Department of Physics and Astronomy, Bucknell University, Lewisburg, PA 17837 (United States); Heger, A.; Meisel, Z.; Smith, K. [Joint Institute for Nuclear Astrophysics (JINA), Michigan State University, East Lansing, MI 48824 (United States); Johnson, E. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

    2016-10-20

    X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to match calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.

  10. Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

    International Nuclear Information System (INIS)

    Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

    2002-01-01

    Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

  11. Influence of inhomogeneous surface heat capacity on the estimation of radiative response coefficients in a two-zone energy balance model

    Science.gov (United States)

    Park, Jungmin; Choi, Yong-Sang

    2018-04-01

    Observationally constrained values of the global radiative response coefficient are pivotal to assess the reliability of modeled climate feedbacks. A widely used approach is to measure transient global radiative imbalance related to surface temperature changes. However, in this approach, a potential error in the estimate of radiative response coefficients may arise from surface inhomogeneity in the climate system. We examined this issue theoretically using a simple two-zone energy balance model. Here, we dealt with the potential error by subtracting the prescribed radiative response coefficient from those calculated within the two-zone framework. Each zone was characterized by the different magnitude of the radiative response coefficient and the surface heat capacity, and the dynamical heat transport in the atmosphere between the zones was parameterized as a linear function of the temperature difference between the zones. Then, the model system was forced by randomly generated monthly varying forcing mimicking time-varying forcing like an observation. The repeated simulations showed that inhomogeneous surface heat capacity causes considerable miscalculation (down to -1.4 W m-2 K-1 equivalent to 31.3% of the prescribed value) in the global radiative response coefficient. Also, the dynamical heat transport reduced this miscalculation driven by inhomogeneity of surface heat capacity. Therefore, the estimation of radiative response coefficients using the surface temperature-radiation relation is appropriate for homogeneous surface areas least affected by the exterior.

  12. Investigations Of Surface-Catalyzed Reactions In A Mars Mixture

    Science.gov (United States)

    Dougherty, Max; Owens, W.; Meyers, J.; Fletcher, D. G.

    2011-05-01

    In the design of a thermal protection system (TPS) for a planetary entry vehicle, accurate modeling of the trajectory aero-heating poses a significant challenge owing to large uncertainties in chemical processes taking place at the surface. Even for surface-catalyzed reactions, which have been investigated extensively, there is no consensus on how they should be modeled; or, in some cases, on which reactions are likely to occur. Current TPS designs for Mars missions rely on a super-catalytic boundary condition, which assumes that all dissociated species recombine to the free stream composition.While this is recognized to be the the most conservative approach, discrepancies in aero-heating measurements in ground test facilities preclude less conservative design options, resulting in an increased TPS mass at the expense of scientific pay- load.Using two-photon absorption laser induced fluorescence in a 30 kW inductively coupled plasma torch facility, preliminary studies have been performed to obtain spatially-resolved measurements of the dominant species in a plasma boundary layer for a Martian atmosphere mixture over catalytic and non-catalytic surfaces.

  13. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones

    DEFF Research Database (Denmark)

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene Mark

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrifica......Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic...... denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off...... Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically...

  14. Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

    Science.gov (United States)

    Beck, Rainer

    2004-03-01

    The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

  15. 22-year surface salinity changes in the Seasonal Ice Zone near 140°E off Antarctica

    Science.gov (United States)

    Morrow, Rosemary; Kestenare, Elodie

    2017-11-01

    Seasonal and interannual variations in sea surface salinity (SSS) are analyzed in the Sea Ice Zone south of 60°S, from a 22-year time series of observations near 140°E. In the northern sea-ice zone during the warming, melting cycle from October to March, waters warm by an average of 3.5 °C and become fresher by 0.1 to 0.25. In the southern sea-ice zone, the surface temperatures vary from - 1 to 1 °C over summer, and the maximal SSS range occurs in December, with a minimum SSS of 33.65 near the Southern Boundary of the ACC, reaching 34.4 in the shelf waters close to the coast. The main fronts, normally defined at subsurface, are shown to have more distinct seasonal characteristics in SSS than in SST. The interannual variations in SSS are more closely linked to variations in upstream sea-ice cover than surface forcing. SSS and sea-ice variations show distinct phases, with large biannual variations in the early 1990s, weaker variations in the 2000s and larger variations again from 2009 onwards. The calving of the Mertz Glacier Tongue in February 2010 leads to increased sea-ice cover and widespread freshening of the surface layers from 2011 onwards. Summer freshening in the northern sea-ice zone is 0.05-0.07 per decade, increasing to 0.08 per decade in the southern sea-ice zone, largely influenced by the Mertz Glacier calving event at the end of our time series. The summer time series of SSS on the shelf at 140°E is in phase but less variable than the SSS observed upstream in the Adélie Depression, and thus represents a spatially integrated index of the wider SSS variations.

  16. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  17. Investigation of heterogeneous reactions of NO2 on aqueous surfaces

    International Nuclear Information System (INIS)

    Mertes, S.

    1992-01-01

    A microjet apparatus was developed for the purpose of measuring the loss in the gaseous phase and the uptake in the liquid phase of nitrogen on the basis of heterogeneous processes on a liquid surface. The measurements were to provide information on the mass accomodation coefficient α and on assumed surface reactions of NO 2 . (orig./BBR) [de

  18. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    International Nuclear Information System (INIS)

    Osborn, David L.

    2017-01-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  19. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    Science.gov (United States)

    Osborn, David L.

    2017-05-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  20. Structure of the 1906 near-surface rupture zone of the San Andreas Fault, San Francisco Peninsula segment, near Woodside, California

    Science.gov (United States)

    Rosa, C.M.; Catchings, R.D.; Rymer, M.J.; Grove, Karen; Goldman, M.R.

    2016-07-08

    High-resolution seismic-reflection and refraction images of the 1906 surface rupture zone of the San Andreas Fault near Woodside, California reveal evidence for one or more additional near-surface (within about 3 meters [m] depth) fault strands within about 25 m of the 1906 surface rupture. The 1906 surface rupture above the groundwater table (vadose zone) has been observed in paleoseismic trenches that coincide with our seismic profile and is seismically characterized by a discrete zone of low P-wave velocities (Vp), low S-wave velocities (Vs), high Vp/Vs ratios, and high Poisson’s ratios. A second near-surface fault strand, located about 17 m to the southwest of the 1906 surface rupture, is inferred by similar seismic anomalies. Between these two near-surface fault strands and below 5 m depth, we observed a near-vertical fault strand characterized by a zone of high Vp, low Vs, high Vp/Vs ratios, and high Poisson’s ratios on refraction tomography images and near-vertical diffractions on seismic-reflection images. This prominent subsurface zone of seismic anomalies is laterally offset from the 1906 surface rupture by about 8 m and likely represents the active main (long-term) strand of the San Andreas Fault at 5 to 10 m depth. Geometries of the near-surface and subsurface (about 5 to 10 m depth) fault zone suggest that the 1906 surface rupture dips southwestward to join the main strand of the San Andreas Fault at about 5 to 10 m below the surface. The 1906 surface rupture forms a prominent groundwater barrier in the upper 3 to 5 m, but our interpreted secondary near-surface fault strand to the southwest forms a weaker barrier, suggesting that there has been less or less-recent near-surface slip on that strand. At about 6 m depth, the main strand of the San Andreas Fault consists of water-saturated blue clay (collected from a hand-augered borehole), which is similar to deeply weathered serpentinite observed within the main strand of the San Andreas Fault at

  1. Reaction of water vapor with a clean liquid uranium surface

    International Nuclear Information System (INIS)

    Siekhaus, W.

    1985-01-01

    To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

  2. Using the Vertical Component of the Surface Velocity Field to Map the Locked Zone at Cascadia Subduction Zone

    Science.gov (United States)

    Moulas, E.; Brandon, M. T.; Podladchikov, Y.; Bennett, R. A.

    2014-12-01

    At present, our understanding of the locked zone at Cascadia subduction zone is based on thermal modeling and elastic modeling of horizontal GPS velocities. The thermal model by Hyndman and Wang (1995) provided a first-order assessment of where the subduction thrust might be cold enough for stick-slip behavior. The alternative approach by McCaffrey et al. (2007) is to use a Green's function that relates horizontal surface velocities, as recorded by GPS, to interseismic elastic deformation. The thermal modeling approach is limited by a lack of information about the amount of frictional heating occurring on the thrust (Molnar and England, 1990). The GPS approach is limited in that the horizontal velocity component is fairly insensitive to the structure of the locked zone. The vertical velocity component is much more useful for this purpose. We are fortunate in that vertical velocities can now be measured by GPS to a precision of about 0.2 mm/a. The dislocation model predicts that vertical velocities should range up to about 20 percent of the subduction velocity, which means maximum values of ~7 mm/a. The locked zone is generally entirely offshore at Cascadia, except for the Olympic Peninsula region, where the underlying Juan De Fuca plate has an anomalously low dip. Previous thermal and GPS modeling, as well as tide gauge data and episodic tremors indicate the locked zone there extends about 50 to 75 km onland. This situation provides an opportunity to directly study the locked zone. With that objective in mind, we have constructed a full 3D geodynamic model of the Cascadia subduction zone. At present, the model provides a full representation of the interseismic elastic deformation due to variations of slip on the subduction thrust. The model has been benchmarked against the Savage (2D) and Okada (3D) analytical solutions. This model has an important advantage over traditional dislocation modeling in that we include temperature-sensitive viscosity for the upper and

  3. Recyclable surfaces for amine conjugation chemistry via redox reaction

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2017-02-15

    In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

  4. Meltwater storage in low-density near-surface bare ice in the Greenland ice sheet ablation zone

    Science.gov (United States)

    Cooper, Matthew G.; Smith, Laurence C.; Rennermalm, Asa K.; Miège, Clément; Pitcher, Lincoln H.; Ryan, Jonathan C.; Yang, Kang; Cooley, Sarah W.

    2018-03-01

    We document the density and hydrologic properties of bare, ablating ice in a mid-elevation (1215 m a.s.l.) supraglacial internally drained catchment in the Kangerlussuaq sector of the western Greenland ice sheet. We find low-density (0.43-0.91 g cm-3, μ = 0.69 g cm-3) ice to at least 1.1 m depth below the ice sheet surface. This near-surface, low-density ice consists of alternating layers of water-saturated, porous ice and clear solid ice lenses, overlain by a thin (sheet ablation zone surface. A conservative estimate for the ˜ 63 km2 supraglacial catchment yields 0.009-0.012 km3 of liquid meltwater storage in near-surface, porous ice. Further work is required to determine if these findings are representative of broader areas of the Greenland ice sheet ablation zone, and to assess the implications for sub-seasonal mass balance processes, surface lowering observations from airborne and satellite altimetry, and supraglacial runoff processes.

  5. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  6. Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

    International Nuclear Information System (INIS)

    Iwaki, T.; Katsuta, K.; Miura, M.

    1981-01-01

    The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

  7. Surface area-burnoff correlation for the steam--graphite reaction

    International Nuclear Information System (INIS)

    Stark, W.A. Jr.; Malinauskas, A.P.

    1977-01-01

    The oxidation of core graphite by steam of air represents a problem area of significant concern in safety analyses for the high temperature gas cooled reactor (HTGR). Core and core-support graphite integrity and strength deteriorate with oxidation of the graphite, and oxidation furthermore could affect the rate of fission product release under upset conditions. Consequently, modeling of core response during steam or air ingress conditions requires an expression for the rate of graphite interaction with those impurities. The steam--graphite reaction in particular is a complex interaction of mass transport within the graphite with chemi-sorption and reaction on accessible surfaces; experimental results from graphite to graphite are highly variable, and the description of the reaction is not yet completely consistent. A simple etch pit model relating surface area to burnoff has been proposed and shown to provide reasonable correlation with experimental data obtained from steam oxidation studies of nuclear grade H-327 graphite. Unaccounted differences between theory and experiment arise at burnoffs exceeding 3 to 5 percent. The model, while not complete nor comprehensive, is consistent with experimental observations of graphite oxidation by O 2 (air), CO 2 , or H 2 O, and could have some utility in safety analysis

  8. Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

    Science.gov (United States)

    Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

    2015-03-25

    Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

  9. The SMAP Level 4 Surface and Root-zone Soil Moisture (L4_SM) Product

    Science.gov (United States)

    Reichle, Rolf; Crow, Wade; Koster, Randal; Kimball, John

    2010-01-01

    The Soil Moisture Active and Passive (SMAP) mission is being developed by NASA for launch in 2013 as one of four first-tier missions recommended by the U.S. National Research Council Committee on Earth Science and Applications from Space in 2007. The primary science objectives of SMAP are to enhance understanding of land surface controls on the water, energy and carbon cycles, and to determine their linkages. Moreover, the high resolution soil moisture mapping provided by SMAP has practical applications in weather and seasonal climate prediction, agriculture, human health, drought and flood decision support. In this paper we describe the assimilation of SMAP observations for the generation of the planned SMAP Level 4 Surface and Root-zone Soil Moisture (L4_SM) product. The SMAP mission makes simultaneous active (radar) and passive (radiometer) measurements in the 1.26-1.43 GHz range (L-band) from a sun-synchronous low-earth orbit. Measurements will be obtained across a 1000 km wide swath using conical scanning at a constant incidence angle (40 deg). The radar resolution varies from 1-3 km over the outer 70% of the swath to about 30 km near the center of the swath. The radiometer resolution is 40 km across the entire swath. The radiometer measurements will allow high-accuracy but coarse resolution (40 km) measurements. The radar measurements will add significantly higher resolution information. The radar is however very sensitive to surface roughness and vegetation structure. The combination of the two measurements allows optimal blending of the advantages of each instrument. SMAP directly observes only surface soil moisture (in the top 5 cm of the soil column). Several of the key applications targeted by SMAP, however, require knowledge of root zone soil moisture (approximately top 1 m of the soil column), which is not directly measured by SMAP. The foremost objective of the SMAP L4_SM product is to fill this gap and provide estimates of root zone soil moisture

  10. Surface reaction rate and probability of ozone and alpha-terpineol on glass, polyvinyl chloride, and latex paint surfaces.

    Science.gov (United States)

    Shu, Shi; Morrison, Glenn C

    2011-05-15

    Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.

  11. Chemical reactions in the presence of surface modulation and stirring

    OpenAIRE

    Kamhawi, Khalid; Náraigh, Lennon Ó

    2009-01-01

    We study the dynamics of simple reactions where the chemical species are confined on a general, time-modulated surface, and subjected to externally-imposed stirring. The study of these inhomogeneous effects requires a model based on a reaction-advection-diffusion equation, which we derive. We use homogenization methods to show that up to second order in a small scaling parameter, the modulation effects on the concentration field are asymptotically equivalent for systems with or without stirri...

  12. Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

    Science.gov (United States)

    Dulnee, Siriwan; Scheinost, Andreas C

    2014-08-19

    To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

  13. Recent Advances in Hyporheic Zone Science

    Science.gov (United States)

    Hester, E. T.

    2017-12-01

    The hyporheic zone exists beneath and adjacent to streams and rivers where surface water and groundwater interact. It provides unique habitat for aquatic organisms, can buffer surface water temperatures, and can be highly reactive, processing nutrients and improving water quality. The hyporheic zone is the subject of considerable research and the past year in WRR witnessed important conceptual advances. A key focus was rigorous evaluation of mixing between surface water and groundwater that occurs within hyporheic sediments. Field observations indicate that greater mixing occurs in the hyporheic zone than in deeper groundwater, and this distinction has been explored by recent numerical modeling studies, but more research is needed to fully understand the causes. A commentary this year in WRR proposed that hyporheic mixing is enhanced by a combination of fluctuating boundary conditions and multiscale physical and chemical spatial heterogeneity but confirmation is left to future research. This year also witnessed the boundaries of knowledge pushed back in a number of other key areas. Field quantification of hyporheic exchange and reactions benefited from advances including the use and interpretation of high frequency nutrient sensors, actively heater fiber optic sensors, isotope tracers, and geophysical methods such as electrical resistivity imaging. Conceptual advances were made in understanding the effects of unsteady environmental conditions (e.g., tides and storms) and preferential flow on hyporheic processes. Finally, hyporheic science is being brought increasingly to bear on applied issues such as informing nutrient removal crediting for stream restoration practices, for example in the Chesapeake Bay watershed.

  14. Surface-induced dissociation and chemical reactions of C2D4(+) on stainless steel, carbon (HOPG), and two different diamond surfaces.

    Science.gov (United States)

    Feketeová, Linda; Zabka, Jan; Zappa, Fabio; Grill, Verena; Scheier, Paul; Märk, Tilmann D; Herman, Zdenek

    2009-06-01

    Surface-induced interactions of the projectile ion C(2)D(4)(+) with room-temperature (hydrocarbon covered) stainless steel, carbon highly oriented pyrolytic graphite (HOPG), and two different types of diamond surfaces (O-terminated and H-terminated) were investigated over the range of incident energies from a few eV up to 50 eV. The relative abundance of the product ions in dependence on the incident energy of the projectile ion [collision-energy resolved mass spectra, (CERMS) curves] was determined. The product ion mass spectra contained ions resulting from direct dissociation of the projectile ions, from chemical reactions with the hydrocarbons on the surface, and (to a small extent) from sputtering of the surface material. Sputtering of the surface layer by low-energy Ar(+) ions (5-400 eV) indicated the presence of hydrocarbons on all studied surfaces. The CERMS curves of the product ions were analyzed to obtain both CERMS curves for the products of direct surface-induced dissociation of the projectile ion and CERMS curves of products of surface reactions. From the former, the fraction of energy converted in the surface collision into the internal excitation of the projectile ion was estimated as 10% of the incident energy. The internal energy of the surface-excited projectile ions was very similar for all studied surfaces. The H-terminated room-temperature diamond surface differed from the other surfaces only in the fraction of product ions formed in H-atom transfer surface reactions (45% of all product ions formed versus 70% on the other surfaces).

  15. Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

    International Nuclear Information System (INIS)

    Amemiya, Kenta

    2015-01-01

    A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

  16. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  17. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  18. Surface and subsurface continuous gravimetric monitoring of groundwater recharge processes through the karst vadose zone at Rochefort Cave (Belgium)

    Science.gov (United States)

    Watlet, A.; Van Camp, M. J.; Francis, O.; Poulain, A.; Hallet, V.; Triantafyllou, A.; Delforge, D.; Quinif, Y.; Van Ruymbeke, M.; Kaufmann, O.

    2017-12-01

    Ground-based gravimetry is a non-invasive and integrated tool to characterize hydrological processes in complex environments such as karsts or volcanoes. A problem in ground-based gravity measurements however concerns the lack of sensitivity in the first meters below the topographical surface, added to limited infiltration below the gravimeter building (umbrella effect). Such limitations disappear when measuring underground. Coupling surface and subsurface gravity measurements therefore allow isolating hydrological signals occurring in the zone between the two gravimeters. We present a coupled surface/subsurface continuous gravimetric monitoring of 2 years at the Rochefort Cave Laboratory (Belgium). The gravity record includes surface measurements of a GWR superconducting gravimeter and subsurface measurements of a Micro-g LaCoste gPhone gravimeter, installed in a cave 35 m below the surface station. The recharge of karstic aquifers is extremely complex to model, mostly because karst hydrological systems are composed of strongly heterogeneous flows. Most of the problem comes from the inadequacy of conventional measuring tools to correctly sample such heterogeneous media, and particularly the existence of a duality of flow types infiltrating the vadose zone: from rapid flows via open conduits to slow seepage through porous matrix. Using the surface/subsurface gravity difference, we were able to identify a significant seasonal groundwater recharge within the karst vadose zone. Seasonal or perennial perched reservoirs have already been proven to exist in several karst areas due to the heterogeneity of the porosity and permeability gradient in karstified carbonated rocks. Our gravimetric experiment allows assessing more precisely the recharge processes of such reservoirs. The gravity variations were also compared with surface and in-cave hydrogeological monitoring (i.e. soil moisture, in-cave percolating water discharges, water levels of the saturated zone). Combined

  19. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  20. Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

    Science.gov (United States)

    Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

    2013-09-01

    In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

  1. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

  2. Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone, New Hampshire, USA

    Science.gov (United States)

    McAleer, Ryan J.; Bish, David L.; Kunk, Michael J.; Sicard, Karri R.; Valley, Peter M.; Walsh, Gregory J.; Wathen, Bryan A.; Wintsch, R.P.

    2016-01-01

    We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na-poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric-forming Na-rich muscovite is also progressively replaced by fabric-forming Na-poor muscovite. The mineralogy of the new phyllonitic fault-rock produced is dominated by Na-poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric-forming Na-rich muscovite is selectively replaced at high-strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high-grade porphyroblasts by weaker Na-poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na-rich muscovite-defined foliation destroys not only the metastable high-grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.

  3. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  4. A theoretical study on the use of microwaves in reducing energy consumption for an endothermic reaction: Role of metal coated bounding surface

    International Nuclear Information System (INIS)

    Bhattacharya, Madhuchhanda; Basak, Tanmay

    2013-01-01

    This work presents a theoretical analysis on savings of energy during an endothermic reaction under microwave heating compared to conventional heating and shows the use of metal coated bounding surface to enhance the energy savings in otherwise low saving zones. Main thrust of this work is the quantification of energy savings for various probable microwave heating scenarios that may arise either due to varying reactor dimension (2L) over thin, intermediate and thick regimes or due to varying dielectric properties of the reactor. The analysis considers detailed transport equations in conjunction with Helmholtz equation for microwave propagation within a semiinfinite batch reactor. Simulations show that use of microwave can significantly save energy (as high as 60%) depending on reactor configuration. Simulations also show efficient use of metal coated bounding surface to enhance energy savings for reactors with 2L/λ eff = 0.5n−0.25, where n = 1, 2, 3… and λ eff is wavelength of microwave within the reactor. The enhancement is found to be 2 and 1.5 times at 2L/λ eff = 0.25 and 0.75, respectively. Various regions of efficient use of metal coated bounding surface for different microwave heating scenarios have been identified in a series of master curves. - Highlights: • This work simulates chemical reaction under microwave radiation using detailed model. • Simulations are presented in presence or absence of metal coated bounding surface. • Savings of energy under microwave have been analyzed for various probable scenarios. • Simulations show significant savings of energy under microwave heating. • Simulations show the potential of metal coated bounding surface to further enhance energy savings

  5. Small leak detection by measuring surface oscillation during sodium-water reaction in steam generator

    International Nuclear Information System (INIS)

    Nei, Hiromichi; Hori, Masao

    1977-01-01

    Small leak sodium-water reaction tests were conducted to develop various kinds of leak detectors for the sodium-heated steam generator in FBR. The super-heated steam was injected into sodium in a reaction vessel having a sodium free surface, simulating the steam generator. The level gauge in the reaction vessel generated the most reliable signal among detectors, as long as the leak rates were relatively high. The level gauge signal was estimated to be the sodium surface oscillation caused by hydrogen bubbles produced in sodium-water reaction. Experimental correlation was derived, predicting the amplitude as a function of leak rate, hydrogen dissolution ratio, bubble rise velocity and other parameters concerned, assuming that the surface oscillation is in proportion to the gas hold-up. The noise amplitude under normal operation without water leak was increased with sodium flow rate and found to be well correlated with Froud number. These two correlations predict that a water leak in a ''MONJU'' class (300 MWe) steam generator could possibly be detected by level gauges at a leak rate above 2 g/sec. (auth.)

  6. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    Science.gov (United States)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  7. IDENTIFICATION OF DANGER ZONES FOR SURFACE WATER USING GIS (SIP – MAPINFO SYSTEM ON AN EXAMPLE OF UPPER NAREW RIVER CATCHMENT

    Directory of Open Access Journals (Sweden)

    Mirosław Skorbiłowicz

    2016-07-01

    Full Text Available Creating the buffer zones is a function intended to designate an area in particular, of a constant distance around the spatial objects. The aim of the study was to create maps as thematic layers, which served to identify areas of existing and potential contamination of surface water and other environmental elements. Among others, it made possible to localize the areas potentially affected by the surface water pollution due to transport; localize the areas potentially affected by the surface water pollution due to the discharge of sewage from human settlements; localize the zones with mitigated impact of communication emissions due to the natural protection of forests taking the form of so-called geochemical barriers. The spatial analyzes allowed to generate model-zones of the existing and potential threat of water pollution in the Narew river catchment. Designated danger zones can be verified by studies as well as they can be very helpful in determining the monitoring network and for water quality modeling process.

  8. Coastal Zone Hazards Related to Groundwater-Surface Water Interactions and Groundwater Flooding

    Science.gov (United States)

    Kontar, Y. A.; Ozorovich, Y. R.; Salokhiddinov, A. T.

    2009-12-01

    Worldwide, as many as half a million people have died in natural and man-made disasters since the turn of the 21st century (Wirtz, 2008). Further, natural and man-made hazards can lead to extreme financial losses (Elsner et al, 2009). Hazards, hydrological and geophysical risk analysis related to groundwater-surface water interactions and groundwater flooding have been to a large extent under-emphasized for coastal zone applications either due to economical limitations or underestimation of its significance. This is particularly true for tsunamis creating salt water intrusion to coastal aquifers, even though most tsunami hazard assessments have in the past relied on scenario or deterministic type models (Geist and Parsons, 2006), and to increasing mineralization of potable water because of intensive water diversions and also the abundance of highly toxic pollutants (mainly pesticides) in water, air and food, which contribute to the deterioration of the coastal population's health (Glantz, 2007). In the wake of pressing environmental and economic issues, it is of prime importance for the scientific community to shed light onto the great efforts by hydrologists and geophysicists to quantify conceptual uncertainties and to provide quality assurances of potential coastal zone hazard evaluation and prediction. This paper proposes consideration of two case studies which are important and significant for future development and essential for feasibility studies of hazards in the coastal zone. The territory of the Aral Sea Region in Central Asia is known as an ecological disaster coastal zone (Zavialov, 2005). It is now obvious that, in order to provide reasonable living conditions to the coastal zone population, it is first of all necessary to drastically improve the quality of the water dedicated to human needs. Due to their intensive pollution by industrial wastes and by drainage waters from irrigated fields, the Syr Darya and Amu Darya rivers can no longer be considered

  9. Assessment of the SMAP Level-4 Surface and Root-Zone Soil Moisture Product Using In Situ Measurements

    NARCIS (Netherlands)

    Reichle, Rolf H.; De Lannoy, Gabrielle J. M.; Liu, Qing; Ardizzone, Joseph V.; Colliander, Andreas; Conaty, Austin; Crow, Wade; Jackson, Thomas J.; Jones, Lucas A.; Kimball, John S.; Koster, Randal D.; Mahanama, Sarith P.; Smith, Edmond B.; Berg, Aaron; Bircher, Simone; Bosch, David; Caldwell, Todd G.; Cosh, Michael; Holifield Collins, Chandra D.; Jensen, Karsten H.; Livingston, Stan; Lopez-baeza, Ernesto; Martínez-fernández, José; Mcnairn, Heather; Moghaddam, Mahta; Pacheco, Anna; Pellarin, Thierry; Prueger, John; Rowlandson, Tracy; Seyfried, Mark; Starks, Patrick; Su, Bob; Thibeault, Marc; Van Der Velde, Rogier; Walker, Jeffrey; Wu, Xiaoling; Zeng, Yijian

    2017-01-01

    The Soil Moisture Active Passive (SMAP) mission Level-4 Surface and Root-Zone Soil Moisture (L4_SM) data product is generated by assimilating SMAP L-band brightness temperature observations into the NASA Catchment land surface model. The L4_SM product is available from 31 March 2015 to present

  10. Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

    Science.gov (United States)

    He, Xin; Kim, Seong H

    2018-02-20

    Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

  11. Surface photo reaction processes using synchrotron radiation; Hoshako reiki ni yoru hyomenko hanno process

    Energy Technology Data Exchange (ETDEWEB)

    Imaizumi, Y. [Tohoku University, Sendai (Japan). Institute for Materials Research; Yoshigoe, A. [Toyohashi University of Technology, Aichi (Japan); Urisu, T. [Toyohashi University of Technology, Aichi (Japan). Institute for Molecular Science

    1997-08-20

    This paper introduces the surface photo reaction processes using synchrotron radiation, and its application. A synchrotron radiation process using soft X-rays contained in electron synchrotron radiated light as an excited light source has a possibility of high-resolution processing because of its short wave length. The radiated light can excite efficiently the electronic state of a substance, and can induce a variety of photochemical reactions. In addition, it can excite inner shell electrons efficiently. In the aspect of its application, it has been found that, if radiated light is irradiated on surfaces of solids under fluorine-based reaction gas or Cl2, the surfaces can be etched. This technology is utilized practically. With regard to radiated light excited CVD process, it may be said that anything that can be deposited by the ordinary plasma CVD process can be deposited. Its application to epitaxial crystal growth may be said a nano processing application in thickness direction, such as forming an ultra-lattice structure, the application being subjected to expectation. In micromachine fabricating technologies, a possibility is searched on application of a photo reaction process of the radiated light. 5 refs., 6 figs.

  12. Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

    The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

  13. The effect of coadsorbed oxygen on the reaction of methanol on Rh(111) and on a rhodium/vanadium surface alloy

    International Nuclear Information System (INIS)

    Schennach, R.; Krenn, G.; Rendulic, K.D.

    2002-01-01

    Full text: Molecular adsorption of methanol can be observed on all transition metal surfaces at low temperatures. Methanol is adsorbed on Rh (111) at 98 K. With increasing methanol exposure first a mono-layer and then multi-layers of methanol are formed at this surface temperature. During heating, desorption of the methanol from physisorbed multi-layers is detected at about 120 K, followed by desorption of methanol from a chemisorbed mono-layer at 170 K. About 50 % of the adsorbed methanol undergoes a dehydrogenation reaction to form hydrogen and carbon monoxide adsorbed on the surface. These reaction products desorb at 300 K and 480 K, respectively. Less than 0.05 monolayers of coadsorbed oxygen increases the amount of methanol that reacts on the surface to about 80 %. Experiments using a Rh/V surface alloy were performed, in order to distinguish between steric and electronic effects in the adsorption and reaction processes. Deposition of 0.3 monolayers of V on the Rh (111) surface leads to the formation of a subsurface alloy, with V atoms in the second atomic layer only. The initial reaction probability was measured as a function of surface temperature and molecular beam energy. A marked difference was found between the two surfaces. On the clean surface methanol adsorption and reaction stops above 198 K, whereas on the alloy surface adsorption and subsequent reaction occurs up to 473 K. The effects of coadsorbed oxygen are similar on both surfaces. The results are discussed in terms of the possible reactions of the adsorbed methanol on the surface. (author)

  14. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  15. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    International Nuclear Information System (INIS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  16. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  17. XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1996-04-01

    The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

  18. Spectral zone selection methodology for pebble bed reactors

    International Nuclear Information System (INIS)

    Mphahlele, Ramatsemela; Ougouag, Abderrafi M.; Ivanov, Kostadin N.; Gougar, Hans D.

    2011-01-01

    A methodology is developed for determining boundaries of spectral zones for pebble bed reactors. A spectral zone is defined as a region made up of a number of nodes whose characteristics are collectively similar and that are assigned the same few-group diffusion constants. The spectral zones are selected in such a manner that the difference (error) between the reference transport solution and the diffusion code solution takes a minimum value. This is achieved by choosing spectral zones through optimally minimizing this error. The objective function for the optimization algorithm is the total reaction rate error, which is defined as the sum of the leakage, absorption and fission reaction rates errors in each zone. The selection of these spectral zones is such that the core calculation results based on diffusion theory are within an acceptable tolerance as compared to a proper transport reference solution. Through this work, a consistent approach for identifying spectral zones that yield more accurate diffusion results is introduced.

  19. Non-thermal desorption from interstellar dust grains via exothermic surface reactions

    Science.gov (United States)

    Garrod, R. T.; Wakelam, V.; Herbst, E.

    2007-06-01

    Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

  20. Geochemical Processes Controlling Migration of High Level Wastes in Hanford's Vadose Zone

    International Nuclear Information System (INIS)

    Zachara, John M.; Serne, R. Jeffrey; Freshley, Mark D.; Mann, Frederick M.; Anderson, Frank J.; Wood, Marcus I.; Jones, Thomas E.; Myers, David A.

    2007-01-01

    High level nuclear wastes (HLW) from Hanford's plutonium reprocessing are stored in massive, buried, single-shell tanks in eighteen tank farms. The wastes were initially hot because of radioactive decay, and many exhibited extreme chemical character in terms of pH, salinity, and radionuclide concentration. At present, 67 of the 149 single shell tanks are suspected to have released over 1.9 million L of tank waste to the vadose zone, with most leak events occurring between 1950 and 1975. Boreholes have been placed through the largest vadose zone plumes to define the extent of contaminant migration, and to develop conceptual models of processes governing the transformation, retardation, and overall transport of tank waste residuals. Laboratory studies with sediments so collected have shown that ion exchange, precipitation and dissolution, and surface complexation reactions have occurred between the HLW and subsurface sediments moderating their chemical character, and retarding the migration of select contaminants. Processes suspected to facilitate the far-field migration of immobile radionuclides including stable aqueous complex formation and mobile colloids were found to be potentially operative, but unlikely to occur in the field, with the exception of cyanide-facilitated migration of 60Co. Fission product oxyanions are the most mobile of tank waste constituents because their adsorption is suppressed by large concentrations of waste anions; the vadose zone clay fraction is negative in surface charge; and, unlike Cr, their reduced forms are unstable in oxidizing environments. Reaction/process-based transport modeling is beginning to be used for predictions of future contaminant mobility and plume evolution

  1. Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers

    International Nuclear Information System (INIS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

    2008-01-01

    The functionalization of surfaces and the ability to tailor their properties with desired physico-chemical functions is an important field of research with a broad spectrum of applications. These applications range from the modification of wetting properties, over the alteration of optical properties, to the fabrication of molecular electronic devices. In each of these fields, it is of specific importance to be able to control the quality of the layers with high precision. The present study demonstrates an approach that utilizes the 1,3-dipolar cycloaddition of terminal acetylenes to prepare triazole-terminated monolayers on different substrates. The characterization of the precursor monolayers, the optimization of the chemical surface reactions as well as the clicking of a fluorescent dye molecule on such azide-terminated monolayers was carried out. A coumarin 343 derivative was utilized to discuss the aspects of the functionalization approach. Based on this approach, a number of potential surface reactions, facilitated via the acetylene-substituted functional molecules, for a broad range of applications is at hand, thus leading to numerous possibilities where surface modifications are concerned. These modifications can be applied on non-structured surfaces of silicon or glass or can be used on structured surfaces. Various possibilities are discussed

  2. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  3. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-06-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  4. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  5. AES study of the reaction between a thin Fe-film and β-SiC (100) surface

    International Nuclear Information System (INIS)

    Mizokawa, Yusuke; Nakanishi, Shigemitsu; Miyase, Sunao

    1989-01-01

    The solid state reaction between thin Fe-films and β-SiC(100) in UHV has been studied using AES. Even at room temperature, the reaction between the thin Fe-film and SiC occurred and formed Fe-silicide and graphite with a minor product of Fe-carbide (Fe 3 C). The reaction proceeded with an increase of Fe-coverage to some extent. With annealing of 15 A-Fe-film/SiC below 540degC, the Fe-silicide formation was accelerated, but because the amount of available Fe was small, the dissolved carbon atoms were forced to form not the Fe-carbide but the graphite phase. Above 640degC, the Fe-silicide started to decompose and the carbon atoms diffused to the surface and formed surface graphite layers. With annealing at 1080degC, the free-Si segregats at the surface and formed Si-Si bonds, as well as the Si-C bonds consuming the surface graphite phase. (author)

  6. Novel ion-molecular surface reaction to result in CH3 adsorbates on (111) surface of chemical vapor deposition diamond from ethane and surface anionic sites

    International Nuclear Information System (INIS)

    Komatsu, Shojiro; Okada, Katsuyuki; Shimizu, Yoshiki; Moriyoshi, Yusuke

    2001-01-01

    The existence of CH 3 adsorbates on (111) surface of chemical vapor deposited diamond, which was observed by scanning tunneling microscopy, was explained by the following S N 2 (bimolecular, substitutional, and nucleophilic) type surface reaction; C(s) - +C 2 H 6 ->C(s)-CH 3 +CH 3 - , where C(s) denotes a surface carbon atom. The activation energy was estimated to be 36.78 kcal/mol and the reaction proved to be exothermic with the enthalpy change of -9.250 kcal/mol, according to ab initio molecular orbital calculations at MP2/3-21+G * //RHF/3-21G * level; this result is consistent with typical substrate temperatures, namely about 900 degree C, for chemical vapor deposition of diamond. Charge transfer from the highest occupied molecular orbital of the surface anionic site to the lowest unoccupied molecular orbital of ethane, that is antibonding at the CH 3 - CH 3 bond, has been clearly visualized. A characteristic configuration of an ethane molecule which is associated with an anionic vacant site C(s) - on hydrogenated (111) surface of diamond was also found. [copyright] 2001 American Institute of Physics

  7. Automatic detection and classification of damage zone(s) for incorporating in digital image correlation technique

    Science.gov (United States)

    Bhattacharjee, Sudipta; Deb, Debasis

    2016-07-01

    Digital image correlation (DIC) is a technique developed for monitoring surface deformation/displacement of an object under loading conditions. This method is further refined to make it capable of handling discontinuities on the surface of the sample. A damage zone is referred to a surface area fractured and opened in due course of loading. In this study, an algorithm is presented to automatically detect multiple damage zones in deformed image. The algorithm identifies the pixels located inside these zones and eliminate them from FEM-DIC processes. The proposed algorithm is successfully implemented on several damaged samples to estimate displacement fields of an object under loading conditions. This study shows that displacement fields represent the damage conditions reasonably well as compared to regular FEM-DIC technique without considering the damage zones.

  8. Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

    Science.gov (United States)

    Chambon, J.; Lemming, G.; Manoli, G.; Broholm, M. M.; Bjerg, P.; Binning, P. J.

    2011-12-01

    Enhanced Reductive Dechlorination (ERD) has been successfully used in high permeability media, such as sand aquifers, and is considered to be a promising technology for low permeability settings. Pilot and full-scale applications of ERD at several sites in Denmark have shown that the main challenge is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion transport processes, and this affects the timeframes for the remediation. Due to the limited ERD applications and the complex transport and reactive processes occurring in low-permeability media, design guidelines are currently not available for ERD in such settings, and remediation performance assessments are limited. The objective of this study is to combine existing knowledge from several sites with numerical modeling to assess the effect of the injection interval, development of bioactive zones and reaction kinetics on the remediation efficiency for ERD in diffusion-dominated media. A numerical model is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities and hydraulic parameters, which are relevant for clay till sites in general. The numerical model couples flow and transport in the fracture network and low-permeability matrix. Sequential degradation of TCE to ethene is modeled using Monod kinetics, and the kinetic parameters are obtained from laboratory experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected

  9. Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

    International Nuclear Information System (INIS)

    Zhao, Shengnan; Liu, Xinhui; Cheng, Dengmiao; Liu, Guannan; Liang, Baocui; Cui, Baoshan; Bai, Junhong

    2016-01-01

    As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L"− "1 and 40.97–207.44 ng·g"− "1, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using the physicochemical

  10. Influence of growth conditions and surface reaction byproducts on GaN grown via metal organic molecular beam epitaxy: Toward an understanding of surface reaction chemistry

    Science.gov (United States)

    Pritchett, David; Henderson, Walter; Burnham, Shawn D.; Doolittle, W. Alan

    2006-04-01

    The surface reaction byproducts during the growth of GaN films via metal organic molecular beam epitaxy (MOMBE) were investigated as a means to optimize material properties. Ethylene and ethane were identified as the dominant surface reaction hydrocarbon byproducts, averaging 27.63% and 7.15% of the total gas content present during growth. Intense ultraviolet (UV) photoexcitation during growth was found to significantly increase the abundance of ethylene and ethane while reducing the presence of H2 and N2. At 920°C, UV excitation was shown to enhance growth rate and crystalline quality while reducing carbon incorporation. Over a limited growth condition range, a 4.5×1019-3.4×1020 cm-3 variation in carbon incorporation was achieved at constant high vacuum. Coupled with growth rate gains, UV excitation yielded films with ˜58% less integrated carbon content. Structural material property variations are reported for various ammonia flows and growth temperatures. The results suggest that high carbon incorporation can be achieved and regulated during MOMBE growth and that in-situ optimization through hydrocarbon analysis may provide further enhancement in the allowable carbon concentration range.

  11. Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

    2017-11-02

    Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

  12. Lean premixed reacting flows with swirl and wall-separation zones in a contracting chamber

    Science.gov (United States)

    Zhang, Yuxin; Rusak, Zvi; Wang, Shixiao

    2017-11-01

    Low Mach number lean premixed reacting swirling flows with wall-separation zones in a contracting circular finite-length open chamber are studied. Assuming a complete reaction with high activation energy and chemical equilibrium behind the reaction zone, a nonlinear partial differential equation is derived for the solution of the flow stream function behind the reaction zone in terms of the inlet total enthalpy for a reacting flow, specific entropy and the circulation functions. Bifurcation diagrams of steady flows are described as the inlet swirl level is increased at fixed chamber contraction and reaction heat release. The approach is applied to an inlet solid-body rotation flow with constant profiles of the axial velocity, temperature and mixture reactant mass fraction. The computed results provide predictions of the critical inlet swirl levels for the first appearance of wall-separation states and for the size of the separation zone as a function of the inlet swirl ratio, Mach number, chamber contraction and heat release of the reaction. The methodology developed in this paper provides a theoretical feasibility for the development of the technology of swirl-assisted combustion where the reaction zone is supported and stabilized by a wall-separation zone.

  13. Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

    Science.gov (United States)

    Sodeau, J.; Oriordan, B.

    2003-04-01

    CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

  14. Acid-base status of soils in groundwater discharge zones — relation to surface water acidification

    Science.gov (United States)

    Norrström, Ann Catrine

    1995-08-01

    Critical load calculations have suggested that groundwater at depth of 2 m in Sweden is very sensitive to acid load. As environmental isotope studies have shown that most of the runoff in streams has passed through the soil, there is a risk in the near future of accelerated acidification of surface waters. To assess the importance of the last soil horizon of contact before discharge, the upper 0-0.2m of soils in seven discharge zones were analysed for pools of base cations, acidity and base saturation. The sites were about 3-4 m 2 in size and selected from two catchments exposed to different levels of acid deposition. The soils in the seven sites had high concentrations of exchangeable base cations and consequently high base saturation. The high correlation ( r2 = 0.74) between base saturation in the soils of the discharge zones and mean pH of the runoff waters suggested that the discharge zone is important for surface water acidification. The high pool of exchangeable base cations will buffer initially against the acid load. As the cation exchange capacity (meq dm -3) and base saturation were lower in the sites from the catchment receiving lower deposition, these streams may be more vulnerable to acidification in the near future. The high concentration of base cations in non-exchangeable fractions may also buffer against acidification as it is likely that some of these pools will become exchangeable with time.

  15. Distribution of Cr atoms in the surface zone of Fe-rich Fe–Cr alloys quenched into various media: Mössbauer spectroscopic study

    International Nuclear Information System (INIS)

    Dubiel, Stanisław M.; Cieślak, Jakub; Żukrowski, Jan

    2015-01-01

    Graphical abstract: Chromium depletion, Δx = x_k − x, in Fe_1_0_0_−_xCr_x (x = 2.2, 3.9, 6.4, 8.5, 10.25, 10.75, 14.9, 15.15) alloys quenched into LN (left panel) and those quenched onto brass (right panel) as found from CEMS (pre surface zone) and TRANS (bulk) Mössbauer spectra (x_k – Cr content in the pre surface or bulk as estimated from the average hyperfine field found for the quenched samples). - Highlights: • Effect of quenching media on Cr atom distribution in Fe–Cr alloys was determined. • Significant differences between bulk and pre surface zone were revealed. • Quenching into water and LH resulted in surface oxidation of samples. • Samples quenched onto a block of brass were not oxidized. - Abstract: Effect of a quenching medium (water, liquid nitrogen and block of brass) on a distribution of Cr atoms in the surface zone of Fe_1_0_0_−_xCr_x (x ≤ 19) alloys was studied with the Mössbauer spectroscopy. The distribution of Cr atoms was expressed in terms of the Cowley–Warren short-range order (SRO) parameters: 〈α_1〉 for the first neighbor-shell, 〈α_2〉 for the second neighbor-shell and 〈α_1_2〉 for both neighbor-shells. It was revealed that none of the quenching media resulted in a random distribution of atoms, yet the degree of randomness was the highest for the samples quenched onto the block of brass. The quenching into water and liquid nitrogen caused a partial oxidation of samples’ surface accompanied by a chromium depletion of the bulk. Quantitative analysis of various phases in the studied samples both in their bulk as well as in pre surface zones was carried out.

  16. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  17. Nanoparticles of noble metals in the supergene zone

    Science.gov (United States)

    Zhmodik, S. M.; Kalinin, Yu. A.; Roslyakov, N. A.; Mironov, A. G.; Mikhlin, Yu. L.; Belyanin, D. K.; Nemirovskaya, N. A.; Spiridonov, A. M.; Nesterenko, G. V.; Airiyants, E. V.; Moroz, T. N.; Bul'bak, T. A.

    2012-04-01

    Formation of noble metal nanoparticles is related to various geological processes in the supergene zone. Dispersed mineral phases appear during weathering of rocks with active participation of microorganisms, formation of soil, in aqueous medium and atmosphere. Invisible gold and other noble metals are incorporated into oxides, hydroxides, and sulfides, as well as in dispersed organic and inorganic carbonic matter. Sulfide minerals that occur in bedrocks and ores unaltered by exogenic processes and in cementation zone are among the main concentrators of noble metal nanoparticles. The ability of gold particles to disaggregate is well-known and creates problems in technological and analytical practice. When Au and PGE nanoparticles and clusters occur, these problems are augmented because of their unusual reactions and physicochemical properties. The studied gold, magnetite, titanomagnetite and pyrite microspherules from cementation zone and clay minerals of laterites in Republic of Guinea widen the knowledge of their abundance and inferred formation conditions, in particular, in the contemporary supergene zone. Morphology and composition of micrometer-sized Au mineral spherules were studied with SEM and laser microprobe. The newly formed segregations of secondary gold on the surface of its residual grains were also an object of investigation. The character of such overgrowths is the most indicative for nanoparticles. The newly formed Au particles provide evidence for redistribution of ultradispersed gold during weathering. There are serious prerequisites to state that microorganisms substantially control unusual nano-sized microspherical morphology of gold particles in the supergene zone. This is supported by experiments indicating active absorption of gold by microorganisms and direct evidence for participation of Ralstonia metallidurans bacteria in the formation of peculiar corroded bacteriomorphic surface of gold grains. In addition, the areas enriched in carbon

  18. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  19. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-04-10

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  20. Study on interfacial reaction between lead-free solders and alternative surface finishes

    International Nuclear Information System (INIS)

    Siti Rabiatul Aisha; Ourdjini, A.; Saliza Osman

    2007-01-01

    This study investigates the interfacial reactions occurring during reflow soldering between Sn-Ag-Cu lead-free solder and two surface finishes: electroless nickel/ immersion gold (ENIG) and immersion silver (IAg). The study focuses on interfacial reactions evolution and growth kinetics of intermetallic compounds (IMC) formed during soldering and isothermal ageing at 150 degree Celsius for up to 2000 hours. Optical and scanning electron microscopy were used to measure IMC thickness and examine the morphology of IMC respectively, whereas the IMC phases were identified by energy dispersive X-ray analysis (EDX). The results showed that the IMC formed on ENIG finish is thinner compared to that formed on IAg finish. For IAg surface finish, Cu 6 Sn 5 IMCs with scallop morphology are formed at the solder/ surface finish interface after reflow while a second IMC, Cu 3 Sn was formed between the copper and Cu 6 Sn 5 IMC after the isothermal ageing treatment. For ENIG surface finish both (Cu,Ni) 6 Sn 5 and (Ni,Cu) 3 Sn 4 are formed after soldering. Isothermal aging of the solder joints formed on ENIG finish was found to have a significant effect on the morphology of the intermetallics by transforming to more spherical and denser morphology in addition to increase i their thickness with increased ageing time. (author)

  1. Statistical mapping of zones of focused groundwater/surface-water exchange using fiber-optic distributed temperature sensing

    Science.gov (United States)

    Mwakanyamale, Kisa; Day-Lewis, Frederick D.; Slater, Lee D.

    2013-01-01

    Fiber-optic distributed temperature sensing (FO-DTS) increasingly is used to map zones of focused groundwater/surface-water exchange (GWSWE). Previous studies of GWSWE using FO-DTS involved identification of zones of focused GWSWE based on arbitrary cutoffs of FO-DTS time-series statistics (e.g., variance, cross-correlation between temperature and stage, or spectral power). New approaches are needed to extract more quantitative information from large, complex FO-DTS data sets while concurrently providing an assessment of uncertainty associated with mapping zones of focused GSWSE. Toward this end, we present a strategy combining discriminant analysis (DA) and spectral analysis (SA). We demonstrate the approach using field experimental data from a reach of the Columbia River adjacent to the Hanford 300 Area site. Results of the combined SA/DA approach are shown to be superior to previous results from qualitative interpretation of FO-DTS spectra alone.

  2. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  3. T-TY Tank Farm Interim Surface Barrier Demonstration - Vadose Zone Monitoring Plan

    International Nuclear Information System (INIS)

    Zhang, Z.F.; Strickland, Christopher E.; Field, Jim G.; Parker, Danny L.

    2010-01-01

    The Hanford Site has 149 underground single-shell tanks that store hazardous radioactive waste. Many of these tanks and their associated infrastructure (e.g., pipelines, diversion boxes) have leaked. Some of the leaked waste has entered the groundwater. The largest known leak occurred from the T-106 Tank of the 241-T Tank Farm in 1973. Five tanks are assumed to have leaked in the TY Farm. Many of the contaminants from those leaks still reside within the vadose zone within the T and TY Tank Farms. The Department of Energy's Office of River Protection seeks to minimize the movement of these contaminant plumes by placing interim barriers on the ground surface. Such barriers are expected to prevent infiltrating water from reaching the plumes and moving them further. The soil water regime is monitored to determine the effectiveness of the interim surface barriers. Soil-water content and water pressure are monitored using off-the-shelf equipment that can be installed by the hydraulic hammer technique. Four instrument nests were installed in the T Farm in fiscal year (FY) 2006 and FY2007; two nests were installed in the TY Farm in FY2010. Each instrument nest contains a neutron probe access tube, a capacitance probe, and four heat-dissipation units. A meteorological station has been installed at the north side of the fence of the T Farm. This document summarizes the monitoring methods, the instrument calibration and installation, and the vadose zone monitoring plan for interim barriers in T farm and TY Farm.

  4. Mapping Deep Low Velocity Zones in Alaskan Arctic Coastal Permafrost using Seismic Surface Waves

    Science.gov (United States)

    Dou, S.; Ajo Franklin, J. B.; Dreger, D. S.

    2012-12-01

    Surface Waves (MASW) suggests the existence of pronounced low shear wave velocity zones that span the depth range of 2 - 30 meters; this zone has shear velocity values comparable to partially thawed soils. Such features coincide with previous findings of very low electrical resistivity structure (as low as ~10 Ohm*m at some locations) from measurements obtained in the first NGEE-Arctic geophysical field campaign (conducted in the week of September 24 - October 1, 2011). These low shear velocity zones are likely representative of regions with high unfrozen water content and thus have important implications on the rate of microbial activity and the vulnerability of deep permafrost carbon pools. Analysis of this dataset required development of a novel inversion approach based on waveform inversion. The existence of multiple closely spaced Rayleigh wave modes made traditional inversion based on mode picking virtually impossible; As a result, we selected a direct misfit evaluation based on comparing dispersion images in the phase velocity/frequency domain. The misfit function was optimized using a global search algorithm, in this case Huyer and Neumaier's Multi Coordinate Search algorithm (MCS). This combination of MCS and waveform misfit allowed recovery of the low velocity region despite the existence of closely spaced modes.

  5. Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

    Science.gov (United States)

    Lynch, Gillian C.; Halvick, Philippe; Zhao, Meishan; Truhlar, Donald G.; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.

    1991-01-01

    Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

  6. Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

    Science.gov (United States)

    Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

    2006-01-01

    Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

  7. Design requirements for ERD in diffusion-dominated media: how do injection interval, bioactive zones and reaction kinetics affect remediation performance?

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Lemming, Gitte; Manoli, Gabriele

    is to get contact between the injected bacteria and electron donor and the contaminants trapped in the low-permeability matrix. Sampling of intact cores from the low-permeability matrix has shown that the bioactive zones (where degradation occurs) are limited in the matrix, due to the slow diffusion...... is developed to simulate ERD at a contaminated site, where the source area (mainly TCE) is located in a clayey till with fractures and interbedded sand lenses. Such contaminated sites are common in North America and Europe. Hydro-geological characterization provided information on geological heterogeneities...... experiments. The influence of the reaction kinetics on remediation efficiency is assessed by varying the biomass concentration of the specific degraders. The injected reactants (donor and bacteria) are assumed to spread in horizontal injection zones of various widths, depending on the development of bioactive...

  8. Effect of Reaction Conditions on the Surface Modification of Cellulose Nanofibrils with Aminopropyl Triethoxysilane

    Directory of Open Access Journals (Sweden)

    Eduardo Robles

    2018-04-01

    Full Text Available Nine different surface modifications of cellulose nanofibrils (CNF with 3-aminopropyl triethoxysilane (ATS by using three different solvent systems (water, ethanol, and a mixture of both were investigated. The effect of reaction conditions, such as silane to cellulose ratio and solvent type were evaluated to determine their contribution to the extent of the silane modification. Nanofibril properties were evaluated by infrared spectroscopy, powder X-ray diffraction, surface free energy, thermogravimetry, 13C and 29Si nuclear magnetic resonance, and electronic microscopy. The influence of the solvent in the solvolysis of the silane was reflected in the presence or absence of ethoxy groups in the silane. On the other hand, whereas the surface modification was increased directly proportionally to silane ratio on the reaction, the aggregation of nanofibrils was also increased, which can play a negative role in certain applications. The increment of silane modification also had substantial repercussions on the crystallinity of the nanofibrils by the addition of amorphous components to the crystalline unit; moreover, silane surface modifications enhanced the hydrophobic character of the nanofibrils.

  9. Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Shengnan [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Liu, Xinhui, E-mail: xhliu@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Cheng, Dengmiao [Institute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing 100081 (China); Liu, Guannan [MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, CAGS, Beijing 100037 (China); Liang, Baocui; Cui, Baoshan; Bai, Junhong [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China)

    2016-11-01

    As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L{sup −} {sup 1} and 40.97–207.44 ng·g{sup −} {sup 1}, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using

  10. Shrinkage Effects of the Conduction Zone in the Electrical Properties of Metal Oxide Nanocrystals: The Basis for Room Temperature Conductometric Gas Sensor

    Directory of Open Access Journals (Sweden)

    M. Manzanares

    2009-01-01

    Full Text Available The influence of charge localized at the surface of minute metal oxide nanocrystals was studied in WO3 and In2O3 nanostructures, which were obtained replicating mesoporous silica templates. Here, it is shown that the very high resistive states observed at room temperature and dark conditions were originated by the total shrinkage of the conductive zone in the inner part of these nanocrystals. On the contrary, at room temperature and under UV illumination, both photogenerated electron-hole pairs and empty surface states generated by photons diminished the negative charge accumulated at the surface, enlarging the conductive zone and, as a consequence, leading to a reduction of the electrical resistance. Under these conditions, empty surface states produced by UV light reacted with oxidizing gaseous molecules. The charge exchange associated to these reactions also affected the size of the inner conductive zone, and leaded to a new steady-state resistance. These chemical, physical and geometrical effects can be used for gas detection, and constitutes the basis for developing novel room temperature conductometric gas sensors responsive to oxidizing species.

  11. Mechanism of formation of a zone without vacancy pores along a surface under electron irradiation of a metal in the high-volt electron microscope

    International Nuclear Information System (INIS)

    Golubov, S.I.; Konobeev, Yu.V.; Ryabov, V.A.

    1981-01-01

    Formation mechanism of zones free of vacancy pores near the vacant surface of a metal preliminary irradiated at a high neutron dose when irradiating with electrons in a high-voltage electron microscope has been suggested. It was assumed to explain experimentally observed values of width and time of such zone formation that interstitial atoms are reflected from foil surface while boundary serves as an ideal sink for the vacancies. The carried out calculation of stationary equations of vacancy and interstitial diffusion with the mentioned boundary condition has shown that determination of a stable zone width is possible only in assumption on a variable in a depth of dislocation density. Theoretical evaluations of a zone width being in good agreement with an experiment and with the results of numerical calculations have been obtained in negligence of recombination of point defects as well as for the case of total reflection of interstitials. Discussed are different mechanisms of weak capture of proper interstitial atoms diffusing to it with the metal surface [ru

  12. VT Data - Zoning 20070306, Marlboro

    Data.gov (United States)

    Vermont Center for Geographic Information — Zoning districts, Marlboro, Vermont. Surface water buffer overlay is in a separate shapefile. Data were originally created by WRC in 2005. Marlboro's zoning bylaw...

  13. Land surface temperature as an indicator of the unsaturated zone thickness: A remote sensing approach in the Atacama Desert.

    Science.gov (United States)

    Urqueta, Harry; Jódar, Jorge; Herrera, Christian; Wilke, Hans-G; Medina, Agustín; Urrutia, Javier; Custodio, Emilio; Rodríguez, Jazna

    2018-01-15

    Land surface temperature (LST) seems to be related to the temperature of shallow aquifers and the unsaturated zone thickness (∆Z uz ). That relationship is valid when the study area fulfils certain characteristics: a) there should be no downward moisture fluxes in an unsaturated zone, b) the soil composition in terms of both, the different horizon materials and their corresponding thermal and hydraulic properties, must be as homogeneous and isotropic as possible, c) flat and regular topography, and d) steady state groundwater temperature with a spatially homogeneous temperature distribution. A night time Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) image and temperature field measurements are used to test the validity of the relationship between LST and ∆Z uz at the Pampa del Tamarugal, which is located in the Atacama Desert (Chile) and meets the above required conditions. The results indicate that there is a relation between the land surface temperature and the unsaturated zone thickness in the study area. Moreover, the field measurements of soil temperature indicate that shallow aquifers dampen both the daily and the seasonal amplitude of the temperature oscillation generated by the local climate conditions. Despite empirically observing the relationship between the LST and ∆Z uz in the study zone, such a relationship cannot be applied to directly estimate ∆Z uz using temperatures from nighttime thermal satellite images. To this end, it is necessary to consider the soil thermal properties, the soil surface roughness and the unseen water and moisture fluxes (e.g., capillarity and evaporation) that typically occur in the subsurface. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. A simple method to assess unsaturated zone time lag in the travel time from ground surface to receptor.

    Science.gov (United States)

    Sousa, Marcelo R; Jones, Jon P; Frind, Emil O; Rudolph, David L

    2013-01-01

    In contaminant travel from ground surface to groundwater receptors, the time taken in travelling through the unsaturated zone is known as the unsaturated zone time lag. Depending on the situation, this time lag may or may not be significant within the context of the overall problem. A method is presented for assessing the importance of the unsaturated zone in the travel time from source to receptor in terms of estimates of both the absolute and the relative advective times. A choice of different techniques for both unsaturated and saturated travel time estimation is provided. This method may be useful for practitioners to decide whether to incorporate unsaturated processes in conceptual and numerical models and can also be used to roughly estimate the total travel time between points near ground surface and a groundwater receptor. This method was applied to a field site located in a glacial aquifer system in Ontario, Canada. Advective travel times were estimated using techniques with different levels of sophistication. The application of the proposed method indicates that the time lag in the unsaturated zone is significant at this field site and should be taken into account. For this case, sophisticated and simplified techniques lead to similar assessments when the same knowledge of the hydraulic conductivity field is assumed. When there is significant uncertainty regarding the hydraulic conductivity, simplified calculations did not lead to a conclusive decision. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  16. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  17. To address surface reaction network complexity using scaling relations machine learning and DFT calculations

    International Nuclear Information System (INIS)

    Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

    2017-01-01

    Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

  18. Dual-zone boiling process

    International Nuclear Information System (INIS)

    Bennett, D.L.; Schwarz, A.; Thorogood, R.M.

    1987-01-01

    This patent describes a process for boiling flowing liquids in a heat exchanger wherein the flowing liquids is heated in a single heat exchanger to vaporize the liquid. The improvement described here comprises: (a) passing the boiling flowing liquid through a first heat transfer zone of the heat exchanger comprising a surface with a high-convective-heat-transfer characteristic and a higher pressure drop characteristic; and then (b) passing the boiling flowing liquid through a second heat transfer zone of the heat exchanger comprising an essentially open channel with only minor obstructions by secondary surfaces, with an enhanced nucleate boiling heat transfer surface and a lower pressure drop characteristic

  19. Evolution of surface motor activation zones in hemiplegic patients during 20 sessions of FES therapy with multi-pad electrodes

    Directory of Open Access Journals (Sweden)

    Jovana Malešević

    2016-06-01

    Full Text Available The purpose of this study was to examine surface motor activation zones for wrist, fingers and thumb extension movements and their temporal change during 20 therapy sessions using advanced multi-pad functional electrical stimulation system. Results from four hemiplegic patients indicate that certain zones have higher probability of eliciting each of the target movements. However, mutual overlap and variations of the zones are present not just between the subjects, but also on the intrasubject level, reflected through these session to session transformations of the selected virtual electrodes. The obtained results could be used as a priori knowledge for semi-automated optimization algorithm and could shorten the time required for calibration of the multi-pad electrode.

  20. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    Science.gov (United States)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  1. The influence of the fault zone width on land surface vibrations after the high-energy tremor in the "Rydułtowy-Anna" hard coal mine

    Science.gov (United States)

    Pilecka, Elżbieta; Szwarkowski, Dariusz

    2018-04-01

    In the article, a numerical analysis of the impact of the width of the fault zone on land surface tremors on the area of the "Rydułtowy - Anna" hard coal mine was performed. The analysis covered the dynamic impact of the actual seismic wave after the high-energy tremor of 7 June 2013. Vibrations on the land surface are a measure of the mining damage risk. It is particularly the horizontal components of land vibrations that are dangerous to buildings which is reflected in the Mining Scales of Intensity (GSI) of vibrations. The run of a seismic wave in the rock mass from the hypocenter to the area's surface depends on the lithology of the area and the presence of fault zones. The rock mass network cut by faults of various widths influences the amplitude of tremor reaching the area's surface. The analysis of the impact of the width of the fault zone was done for three alternatives.

  2. Molecular resonances, fusion reactions and surface transparency of interaction between heavy ions

    International Nuclear Information System (INIS)

    Abe, Yasuhisa.

    1980-01-01

    A review of the Band Crossing Model is given, including recent results on the 16 O + 16 O system. Surface Transparency is discussed in the light of the recent development in our understanding of the fusion reaction mechanisms and by calculating the number of open channels available to direct reactions. The existence of the Molecular Resonance Region is suggested in several systems by the fact that Band Crossing Region overlaps with the Transparent Region. A systematic study predicts molecular resonances in the 14 C + 14 C and 12 C + 14 C systems as prominent as those observed in the 16 O + 16 O and 12 C + 16 O systems

  3. Surface Modification Reaction of Photocatalytic Titanium Dioxide with Triethoxysilane for Improving Dispersibility

    International Nuclear Information System (INIS)

    Lee, Myung Jin; Kim, Ji Ho; Park, Young Tae

    2010-01-01

    We have carried out the surface modification of photocatalytic TiO 2 with triethoxysilane through dehydrogenation reaction and characterized the modified photocatalyst by spectroscopic methods, such as FT-IR, solid-state 29 Si MAS NMR, XPS, and XRF, etc. We also examined photocatalytic activity of the immobilized photocatalytic titanium dioxide with triethoxysilane by decolorization reaction of dyes such as cong red and methylene blue under visible light. Dispersion test showed that the photocatalytic titanium dioxide immobilized with triethoxysilane group has kept higher dispersibility than titanium dioxide itself. No appreciable precipitation takes place even after standing for 24 h in the 4:6 mixture ratio of ethanol and water

  4. Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

    DEFF Research Database (Denmark)

    Olsen, Thomas; Schiøtz, Jakob

    2009-01-01

    A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such...... density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....

  5. Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.

    Science.gov (United States)

    Gao, Erping; Wang, Wenzhong

    2013-11-21

    Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2˙(-) anions as the major oxidation species instead of ˙OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25.

  6. Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

    Science.gov (United States)

    Liu, Xuyang; Ray, Jessica R; Neil, Chelsea W; Li, Qingyun; Jun, Young-Shin

    2015-05-05

    Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

  7. Adsorption of water vapour and the specific surface area of arctic zone soils (Spitsbergen)

    Science.gov (United States)

    Cieśla, Jolanta; Sokołowska, Zofia; Witkowska-Walczak, Barbara; Skic, Kamil

    2018-01-01

    Water vapour/nitrogen adsorption were investigated and calculated the specific surface areas of arctic-zone soil samples (Turbic Cryosols) originating from different micro-relief forms (mud boils, cell forms and sorted circles) and from different depths. For the characterisation of the isotherms obtained for arctic soils, the Brunauer-Emmet-Teller model was then compared with the two other models (Aranovich-Donohue and Guggenheim-Anderson-de Boer) which were developed from Brunauer-Emmet-Teller. Specific surface area was calculated using the Brunauer-Emmet-Teller model at p p0-1 range of 0.05-0.35 for the water vapour desorption and nitrogen adsorption isotherms. The values of total specific surface area were the highest in Cryosols on mud boils, lower on cell forms, and the lowest on sorted circles. Such tendency was observed for the results obtained by both the water vapour and nitrogen adsorption. The differences in the values of specific surface area at two investigated layers were small. High determination coefficients were obtained for relationships between the specific surface areas and contents of clay and silt fraction in Cryosols. No statistically significant correlation between the total carbon amount and the values of specific surface area in Cryosols has been found.

  8. A parametric investigation of hydrogen hcci combustion using a multi-zone model approach

    International Nuclear Information System (INIS)

    Komninos, N.P.; Hountalas, D.T.; Rakopoulos, C.D.

    2007-01-01

    The purpose of the present study is to examine the effect of various operating variables of a homogeneous charge compression ignition (HCCI) engine fueled with hydrogen, using a multi-zone model developed by the authors. The multi-zone model consists of zones, which are allotted spatial locations within the combustion chamber. The model takes into account heat transfer between the zones and the combustion chamber walls, providing a spatial temperature distribution during the closed part of the engine cycle, i.e. compression, combustion and expansion. Mass transfer between zones is also accounted for, based on the geometric configuration of the zones, and includes the flow of mass in and out of the crevice regions, represented by the crevice zone. Combustion is incorporated using chemical kinetics based on a chemical reaction mechanism for the oxidation of hydrogen. This chemical reaction mechanism also includes the reactions for nitrogen oxides formation. Using the multi-zone model a parametric investigation is conducted, in order to determine the effect of engine speed, equivalence ratio, compression ratio, inlet pressure and inlet temperature, on the performance, combustion characteristics and emissions of an HCCI engine fueled with hydrogen

  9. Investigations of chemical reactions between U-Zr alloy and FBR cladding materials

    International Nuclear Information System (INIS)

    Ishii, Tetsuya; Ukai, Shigeharu

    2005-07-01

    U-Pu-Zr alloys are candidate materials for commercial FBR fuel. However, informations about chemical reactions with cladding materials developed by JNC for commercial FBR have not been well obtained. In this work, the reaction zones formed in four diffusion couples U-10wt.%Zr/PNC-FMS, U-10wt.%Zr/9Cr-ODS, U-10wt.%Zr/12Cr-ODS, and U-10wt.%Zr/Fe at about 1013K have been examined and following results were obtained. 1) At about 1013K, in the U-10wt.%Zr/Fe couple, the liquid phase zones were obtained. In the other couples U-10wt.%Zr/PNC-FMS, U-10wt.%Zr/9Cr-ODS and U-10wt.%Zr/12Cr-ODS, no liquid phase zones were obtained. The obtained chemical reaction zones in the later 3 couples were similar to the reported ones obtained in U-Zr/Fe couples without liquid phase formation. In comparison with the reaction zones obtained in the U-10wt.%Zr/Fe couple, the reaction zones inside cladding materials obtained in the PNC-FMS, 9Cr-ODS, and 12Cr-ODS couples were thin. 2) From the investigations of relationship between the obtained depths of the chemical reaction zones inside cladding materials and composition of the cladding materials, it was considered that the depth of chemical reaction zone would depend on the Cr content of the cladding materials and the depth would decrease with increasing Cr content, resulting in prevention of liquid phase formation. 3) From the investigations of the mechanisms of chemical reactions between U-Pu-Zr/cladding materials, it was considered that the same effect of Cr obtained in the U-Zr/cladding materials would be expected in U-Pu-Zr/cladding materials. Those seemed to indicate that the threshold temperatures of liquid phase formation for U-Pu-Zr/PNC-FMS, U-Pu-Zr/9Cr-ODS, and U-Pu-Zr/12Cr-ODS might be higher than that for U-Pu-Zr/Fe. (author)

  10. In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

    International Nuclear Information System (INIS)

    Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

    2012-01-01

    Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

  11. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  12. Spatio-temporal Root Zone Soil Moisture Estimation for Indo - Gangetic Basin from Satellite Derived (AMSR-2 and SMOS) Surface Soil Moisture

    Science.gov (United States)

    Sure, A.; Dikshit, O.

    2017-12-01

    Root zone soil moisture (RZSM) is an important element in hydrology and agriculture. The estimation of RZSM provides insight in selecting the appropriate crops for specific soil conditions (soil type, bulk density, etc.). RZSM governs various vadose zone phenomena and subsequently affects the groundwater processes. With various satellite sensors dedicated to estimating surface soil moisture at different spatial and temporal resolutions, estimation of soil moisture at root zone level for Indo - Gangetic basin which inherits complex heterogeneous environment, is quite challenging. This study aims at estimating RZSM and understand its variation at the level of Indo - Gangetic basin with changing land use/land cover, topography, crop cycles, soil properties, temperature and precipitation patterns using two satellite derived soil moisture datasets operating at distinct frequencies with different principles of acquisition. Two surface soil moisture datasets are derived from AMSR-2 (6.9 GHz - `C' Band) and SMOS (1.4 GHz - `L' band) passive microwave sensors with coarse spatial resolution. The Soil Water Index (SWI), accounting for soil moisture from the surface, is derived by considering a theoretical two-layered water balance model and contributes in ascertaining soil moisture at the vadose zone. This index is evaluated against the widely used modelled soil moisture dataset of GLDAS - NOAH, version 2.1. This research enhances the domain of utilising the modelled soil moisture dataset, wherever the ground dataset is unavailable. The coupling between the surface soil moisture and RZSM is analysed for two years (2015-16), by defining a parameter T, the characteristic time length. The study demonstrates that deriving an optimal value of T for estimating SWI at a certain location is a function of various factors such as land, meteorological, and agricultural characteristics.

  13. Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations.

    Science.gov (United States)

    Peretz-Soroka, Hagit; Pevzner, Alexander; Davidi, Guy; Naddaka, Vladimir; Kwiat, Moria; Huppert, Dan; Patolsky, Fernando

    2015-07-08

    Significant research efforts have been dedicated to the integration of biological species with electronic elements to yield smart bioelectronic devices. The integration of DNA, proteins, and whole living cells and tissues with electronic devices has been developed into numerous intriguing applications. In particular, the quantitative detection of biological species and monitoring of biological processes are both critical to numerous areas of medical and life sciences. Nevertheless, most current approaches merely focus on the "monitoring" of chemical processes taking place on the sensing surfaces, and little efforts have been invested in the conception of sensitive devices that can simultaneously "control" and "monitor" chemical and biological reactions by the application of on-surface reversible stimuli. Here, we demonstrate the light-controlled fine modulation of surface pH by the use of photoactive molecularly modified nanomaterials. Through the use of nanowire-based FET devices, we showed the capability of modulating the on-surface pH, by intensity-controlled light stimulus. This allowed us simultaneously and locally to control and monitor pH-sensitive biological reactions on the nanodevices surfaces, such as the local activation and inhibition of proteolytic enzymatic processes, as well as dissociation of antigen-antibody binding interactions. The demonstrated capability of locally modulating the on-surface effective pH, by a light stimuli, may be further applied in the local control of on-surface DNA hybridization/dehybridization processes, activation or inhibition of living cells processes, local switching of cellular function, local photoactivation of neuronal networks with single cell resolution and so forth.

  14. Reaction dynamics of small molecules at metal surfaces

    International Nuclear Information System (INIS)

    Samson, P.A.

    1999-09-01

    The dissociation-desorption dynamics of D 2 upon the Sn/Pt(111) surface alloy are dependent on the surface concentration of Sn. The p(2 x 2) Sn/Pt(111) alloy surface (Θ Sn = 0.25 ML), is initially ∼30 times less reactive towards D 2 adsorption than clean Pt(111). On the (√3 x √3) R30 deg Sn/Pt(111) alloy surface (Θ Sn = 0.33 ML), increased inhibition of D 2 adsorption is reported, with S o ∼ 10 -5 at low energy, coinciding with the loss of stable Pt 3 hollow sites and a significant reduction in the D atom binding energy. Sticking on the √3 alloy is activated with an increased energy threshold of ∼280 meV, with no evidence that vibration enhances dissociation. The barrier to dissociation remains in the entrance channel before the D 2 bond begins to stretch. Vibrational excitation is, however, observed in nitrogen desorption from the catalytic reaction of NO + H 2 over Pd(110). For a surface at 600 K, N 2 vibrational state population ratios of P(v=1/v=0) = 0.50 ± 0.05 and P(v=2/v=0) = 0.60 ± 0.20 are reported. Desorption occurs via the N(ad) + N(ad) recombination channel with little energy released into translation and rotation. The translational energy release observed is dependent on the N 2 vibrational state, with translational temperatures of 425 K, 315 K and 180 K reported for the v=0, 1 and 2 states respectively. Sub-thermal energy releases and normally directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d NN responsible for the product vibrational excitation. Although N 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (∼10 -6 to 10 -7 ). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe 4 N. Scanning tunnelling

  15. Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time.

    Science.gov (United States)

    Thompson, Katherine C; Rennie, Adrian R; King, Martin D; Hardman, Samantha J O; Lucas, Claire O M; Pfrang, Christian; Hughes, Brian R; Hughes, Arwel V

    2010-11-16

    The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

  16. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  17. Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

    International Nuclear Information System (INIS)

    Zhang Weiguo; Feng Huan; Chang Jinna; Qu Jianguo; Xie Hongxia; Yu Lizhong

    2009-01-01

    Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg -1 dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I geo ) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn. - Surface sediment metal enrichment is evidenced for Cd, Cr and Ni in the Yangtze River intertidal zone.

  18. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  19. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    2012-01-01

    Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone. In the ......Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone....... In the present paper different aspects of the pozzolanic reaction of silica fume are investigated. These include chemical shrinkage, isothermal heat development and strength development. Key data for these are given and compared with theoretical calculations, and based on presented measurements the energy...

  20. Continuous processing of polymers in repetitively pulsed atmospheric pressure discharges with moving surfaces and gas flow

    Energy Technology Data Exchange (ETDEWEB)

    Bhoj, Ananth N [Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL 61801 (United States); Kushner, Mark J [Department of Electrical and Computer Engineering, Iowa State University, Ames, IA 50011 (United States)

    2007-11-21

    Atmospheric pressure corona discharges are industrially employed to treat large areas of commodity polymer sheets by creating new surface functional groups. The most common processes use oxygen containing discharges to affix oxygen to hydrocarbon polymers, thereby increasing their surface energy and wettability. The process is typically continuous and is carried out in a web configuration with film speeds of tens to hundreds of cm s{sup -1}. The densities and relative abundances of functional groups depend on the gas composition, gas flow rate and residence time of the polymer in the discharge zone which ultimately determine the magnitude and mole fractions of reactive fluxes to the surface. In this paper, results are discussed from a two-dimensional computational investigation of the atmospheric pressure plasma functionalization of a moving polypropylene sheet in repetitively pulsed He/O{sub 2}/H{sub 2}O discharges. O and OH typically initiate surface processing by hydrogen abstraction. These species are regenerated during every plasma pulse but are also largely consumed during the inter-pulse period. Longer-lived species such as O{sub 3} accumulate over many pulses and convect downstream with the gas flow. Optimizing the interplay between local rapid reactions, such as H abstraction which occurs dominantly in the discharge zone, and non-local slower processes, such as surface-surface reactions, may enable the customization of the relative abundance of surface functional groups.

  1. Continuous processing of polymers in repetitively pulsed atmospheric pressure discharges with moving surfaces and gas flow

    International Nuclear Information System (INIS)

    Bhoj, Ananth N; Kushner, Mark J

    2007-01-01

    Atmospheric pressure corona discharges are industrially employed to treat large areas of commodity polymer sheets by creating new surface functional groups. The most common processes use oxygen containing discharges to affix oxygen to hydrocarbon polymers, thereby increasing their surface energy and wettability. The process is typically continuous and is carried out in a web configuration with film speeds of tens to hundreds of cm s -1 . The densities and relative abundances of functional groups depend on the gas composition, gas flow rate and residence time of the polymer in the discharge zone which ultimately determine the magnitude and mole fractions of reactive fluxes to the surface. In this paper, results are discussed from a two-dimensional computational investigation of the atmospheric pressure plasma functionalization of a moving polypropylene sheet in repetitively pulsed He/O 2 /H 2 O discharges. O and OH typically initiate surface processing by hydrogen abstraction. These species are regenerated during every plasma pulse but are also largely consumed during the inter-pulse period. Longer-lived species such as O 3 accumulate over many pulses and convect downstream with the gas flow. Optimizing the interplay between local rapid reactions, such as H abstraction which occurs dominantly in the discharge zone, and non-local slower processes, such as surface-surface reactions, may enable the customization of the relative abundance of surface functional groups

  2. Microanalysis of solid surfaces by nuclear reactions and elastic scattering

    International Nuclear Information System (INIS)

    Agius, B.

    1975-01-01

    The principles involved in the use of monokinetic light ions beams, of about 1MeV, to the study of surface phenomena are presented. Two complementary techniques are described: the use of elastic scattering, which allows the analysis of impurity elements heavier than the substrate components and the use of nuclear reactions specific of light elements. Typical sensitivities are of the order of 10 11 at/cm 2 in good cases. The depth resolution varies, according to the cases, from about a hundred angstroems to a few thousand angstroems [fr

  3. Surface wave tomography across the Sorgenfrei-Tornquist Zone, SW Scandinavia, using ambient noise and earthquake data

    Science.gov (United States)

    Köhler, Andreas; Maupin, Valérie; Balling, Niels

    2015-10-01

    We produce a S-wave velocity model of the crust and upper mantle around the Sorgenfrei-Tornquist Zone, southern Scandinavia, by analysing ambient seismic noise and earthquake recordings on temporary and permanent regional network stations. In a first step, we perform tomographical inversion of surface wave dispersion data from seismic noise to obtain Rayleigh and Love wave phase-velocity maps from 3 to about 30 s period. Local dispersion curves are then combined with regionally averaged surface wave velocities from earthquake data measured between 15 and about 100 s period. Dispersion curves are jointly inverted for a 3-D model of the S-wave velocity and radial velocity anisotropy by using a combined Monte Carlo and linearized inversion approach. Results reveal significant crustal as well as uppermost mantle velocity variations at all depth levels. Upper crustal structural variations are mainly controlled by the thick sedimentary Danish Basin with both low S-wave velocities and high anisotropy. Despite of the known limited capability of surface wave inversion to constrain interface depths and model parameter trade-offs, obtained Moho depths are in good agreement with previous studies in the region. Marked crustal thinning is clearly revealed beneath the Danish Basin with a narrow transition to the thicker crust in Swedish shield areas. Despite very different crustal and morphological structures, Denmark and southern Norway both have similar well-defined upper-mantle low-velocity zones, interpreted as asthenosphere, starting a depth of about 100 km. Compared with southern Sweden, showing high upper-mantle velocities, characteristic for shields, velocities are reduced by 0.30-0.40 km s-1 (6-8 per cent) at the depth levels of 140-200 km and radial anisotropy of 2-4 per cent is observed. Our study confirms the importance of the Sorgenfrei-Tornquist Zone, as a very deep structural boundary, separating old, thick, cratonic Baltica lithosphere in southern Sweden from

  4. Surface elevation change and susceptibility of different mangrove zones to sea-level rise on Pacific high islands of Micronesia

    Science.gov (United States)

    Krauss, K.W.; Cahoon, D.R.; Allen, J.A.; Ewel, K.C.; Lynch, J.C.; Cormier, N.

    2010-01-01

    Mangroves on Pacific high islands offer a number of important ecosystem services to both natural ecological communities and human societies. High islands are subjected to constant erosion over geologic time, which establishes an important source of terrigeneous sediment for nearby marine communities. Many of these sediments are deposited in mangrove forests and offer mangroves a potentially important means for adjusting surface elevation with rising sea level. In this study, we investigated sedimentation and elevation dynamics of mangrove forests in three hydrogeomorphic settings on the islands of Kosrae and Pohnpei, Federated States of Micronesia (FSM). Surface accretion rates ranged from 2.9 to 20.8 mm y-1, and are high for naturally occurring mangroves. Although mangrove forests in Micronesian high islands appear to have a strong capacity to offset elevation losses by way of sedimentation, elevation change over 61/2 years ranged from -3.2 to 4.1 mm y-1, depending on the location. Mangrove surface elevation change also varied by hydrogeomorphic setting and river, and suggested differential, and not uniformly bleak, susceptibilities among Pacific high island mangroves to sea-level rise. Fringe, riverine, and interior settings registered elevation changes of -1.30, 0.46, and 1.56 mm y-1, respectively, with the greatest elevation deficit (-3.2 mm y-1) from a fringe zone on Pohnpei and the highest rate of elevation gain (4.1 mm y-1) from an interior zone on Kosrae. Relative to sea-level rise estimates for FSM (0.8-1.8 mm y-1) and assuming a consistent linear trend in these estimates, soil elevations in mangroves on Kosrae and Pohnpei are experiencing between an annual deficit of 4.95 mm and an annual surplus of 3.28 mm. Although natural disturbances are important in mediating elevation gain in some situations, constant allochthonous sediment deposition probably matters most on these Pacific high islands, and is especially helpful in certain hydrogeomorphic zones

  5. The Effect of Simulated Microgravity Environment of RWV Bioreactors on Surface Reactions and Adsorption of Serum Proteins on Bone-bioactive Microcarriers

    Science.gov (United States)

    Radin, Shula; Ducheyne, P.; Ayyaswamy, P. S.

    2003-01-01

    Biomimetically modified bioactive materials with bone-like surface properties are attractive candidates for use as microcarriers for 3-D bone-like tissue engineering under simulated microgravity conditions of NASA designed rotating wall vessel (RWV) bioreactors. The simulated microgravity environment is attainable under suitable parametric conditions of the RWV bioreactors. Ca-P containing bioactive glass (BG), whose stimulatory effect on bone cell function had been previously demonstrated, was used in the present study. BG surface modification via reactions in solution, resulting formation of bone-like minerals at the surface and adsorption of serum proteins is critical for obtaining the stimulatory effect. In this paper, we report on the major effects of simulated microgravity conditions of the RWV on the BG reactions surface reactions and protein adsorption in physiological solutions. Control tests at normal gravity were conducted at static and dynamic conditions. The study revealed that simulated microgravity remarkably enhanced reactions involved in the BG surface modification, including BG dissolution, formation of bone-like minerals at the surface and adsorption of serum proteins. Simultaneously, numerical models were developed to simulate the mass transport of chemical species to and from the BG surface under normal gravity and simulated microgravity conditions. The numerical results showed an excellent agreement with the experimental data at both testing conditions.

  6. Small-Scale Surf Zone Geometric Roughness

    Science.gov (United States)

    2017-12-01

    using stereo imagery techniques. A waterproof two- camera system with self-logging and internal power was developed using commercial-off-the-shelf...estimates. 14. SUBJECT TERMS surface roughness, nearshore, aerodynamic roughness, surf zone, structure from motion, 3D imagery 15. NUMBER OF... power was developed using commercial-off-the- shelf components and commercial software for operations 1m above the sea surface within the surf zone

  7. DEEP VADOSE ZONE TREATABILITY TEST PLAN

    International Nuclear Information System (INIS)

    Chronister, G.B.; Truex, M.J.

    2009-01-01

    (sm b ullet) Treatability test plan published in 2008 (sm b ullet) Outlines technology treatability activities for evaluating application of in situ technologies and surface barriers to deep vadose zone contamination (technetium and uranium) (sm b ullet) Key elements - Desiccation testing - Testing of gas-delivered reactants for in situ treatment of uranium - Evaluating surface barrier application to deep vadose zone - Evaluating in situ grouting and soil flushing

  8. Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

    Science.gov (United States)

    Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

    1992-01-01

    A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois. Chemical data were evaluated to determine the principal naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on- site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rain water or snowmelt changed to an ionic canposition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The

  9. Surface and microstructure modifications of Ti-6Al-4V titanium alloy cutting by a water jet/high power laser converging coupling

    Science.gov (United States)

    Weiss, Laurent; Tazibt, Abdel; Aillerie, Michel; Tidu, Albert

    2018-01-01

    The metallurgical evolution of the Ti-6Al-4V samples is analyzed after an appropriate cutting using a converging water jet/high power laser system. New surface microstructures are obtained on the cutting edge as a result of thermo-mechanical effects of such hybrid fluid-jet-laser tool on the targeted material. The laser beam allows to melt and the water-jet to cool down and to evacuate the material upstream according to a controlled cutting process. The experimental results have shown that a rutile layer can be generated on the surface near the cutting zone. The recorded metallurgical effect is attributed to the chemical reaction between water molecules and titanium, where the laser thermal energy brought onto the surface plays the role of reaction activator. The width of the oxidized zone was found proportional to the cutting speed. During the reaction, hydrogen gas H2 is formed and is absorbed by the metal. The hydrogen atoms trapped into the alloy change the metastable phase formation developing pure β circular grains as a skin at the kerf surface. This result is original so it would lead to innovative converging laser water jet process that could be used to increase the material properties especially for surface treatment, a key value of surface engineering and manufacturing chains.

  10. Rate of Isotope Exchange Reaction Between Tritiated Water in a Gas Phase and Water on the Surface of Piping Materials

    International Nuclear Information System (INIS)

    Nakashio, Nobuyuki; Yamaguchi, Junya; Kobayashi, Ryusuke; Nishikawa, Masabumi

    2001-01-01

    The system effect of tritium arises from the interaction of tritium in the gas phase with water on the surface of piping materials. It has been reported that the system effect can be quantified by applying the serial reactor model to the piping system and that adsorption and isotope exchange reactions play the main roles in the trapping of tritium. The isotope exchange reaction that occurs when the chemical form of tritium in the gas phase is in the molecular form, i.e., HT or T 2 , has been named isotope exchange reaction 1, and that which occurs when tritium in the gas phase is in water form, i.e., HTO or T 2 O, has been named isotope exchange reaction 2.The rate of isotope exchange reaction 2 is experimentally quantified, and the rate is observed to be about one-third of the rate of adsorption. The trapping and release behavior of tritium from the piping surface due to isotope exchange reaction 2 is also discussed. It is certified that swamping of water vapor to process gas is effective to release tritium from the surface contaminated with tritium

  11. On-surface synthesis on a bulk insulator surface

    Science.gov (United States)

    Richter, Antje; Floris, Andrea; Bechstein, Ralf; Kantorovich, Lev; Kühnle, Angelika

    2018-04-01

    On-surface synthesis has rapidly emerged as a most promising approach to prepare functional molecular structures directly on a support surface. Compared to solution synthesis, performing chemical reactions on a surface offers several exciting new options: due to the absence of a solvent, reactions can be envisioned that are otherwise not feasible due to the insolubility of the reaction product. Perhaps even more important, the confinement to a two-dimensional surface might enable reaction pathways that are not accessible otherwise. Consequently, on-surface synthesis has attracted great attention in the last decade, with an impressive number of classical reactions transferred to a surface as well as new reactions demonstrated that have no classical analogue. So far, the majority of the work has been carried out on conducting surfaces. However, when aiming for electronic decoupling of the resulting structures, e.g. for the use in future molecular electronic devices, non-conducting surfaces are highly desired. Here, we review the current status of on-surface reactions demonstrated on the (10.4) surface of the bulk insulator calcite. Besides thermally induced C-C coupling of halogen-substituted aryls, photochemically induced [2  +  2] cycloaddition has been proven possible on this surface. Moreover, experimental evidence exists for coupling of terminal alkynes as well as diacetylene polymerization. While imaging of the resulting structures with dynamic atomic force microscopy provides a direct means of reaction verification, the detailed reaction pathway often remains unclear. Especially in cases where the presence of metal atoms is known to catalyze the corresponding solution chemistry reaction (e.g. in the case of the Ullmann reaction), disclosing the precise reaction pathway is of importance to understand and generalize on-surface reactivity on a bulk insulator surface. To this end, density-functional theory calculations have proven to provide atomic

  12. Sodium-concrete reaction model development

    International Nuclear Information System (INIS)

    Nguyen, D.H.; Muhlestein, L.D.; Postma, A.K.

    1982-07-01

    Major observations have been formulated after reviewing test results for over 100 sodium-concrete reaction tests. The observations form the basis for developing a mechanistic model to predict the transient behavior of sodium-concrete reactions. The major observations are listed. Mechanisms associated with sodium and water transport to the reaction zone are identified, and represented by appropriate mathematical expressions. The model attempts to explain large-scale, long-term (100 h) test results were sodium-concrete reactions terminated even in the presence of unreacted sodium and concrete

  13. Groundwater monitoring and modelling of the “Vector” site for near-surface radioactive waste disposal in the Chornobyl exclusion zone

    Directory of Open Access Journals (Sweden)

    D. Bugai

    2017-12-01

    Full Text Available Results of purposeful groundwater monitoring and modelling studies are presented, which were carried out in order to better understand groundwater flow patterns from the “Vector” site for near-surface radioactive waste disposal and storage in the Chornobyl exclusion zone towards river network. Both data of observations at local-scale monitoring well network at “Vector” site carried out in 2015 - 2016 and modelling analyses using the regional groundwater flow model of Chornobyl exclusion zone suggest that the groundwater discharge contour for water originating from “Vector” site is Sakhan River, which is the tributary to Pripyat River. The respective groundwater travel time is estimated at 210 - 340 years. The travel times in subsurface for 90Sr, 137Cs, and transuranium radionuclides (Pu isotopes, 241Am are estimated respectively at thousands, tenths of thousands, hundreds of thousands – million of years. These results, as well as presented data of analyses of lithological properties of the geological deposits of the unsaturated zone at “Vector” site, provide evidence for good protection of surface water resources from radioactivity sources (e.g., radioactive wastes to be disposed in the near-sursface facilities at “Vector” site.

  14. Deciduous Forest Zone of Ghana

    African Journals Online (AJOL)

    carbon, nitrogen and phosphorus contents, soil reaction and base saturation with highest values in the topsoil due to the .... These soils occur extensively in the. Zone ... tion with 6M sulphuric acid. .... which will lead to removal of topsoil litter,.

  15. T Tank Farm Interim Surface Barrier Demonstration--Vadose Zone Monitoring Plan

    International Nuclear Information System (INIS)

    Zhang, Z. F.; Keller, Jason M.; Strickland, Christopher E.

    2007-01-01

    The Hanford Site has 149 underground single-shell tanks that store hazardous radioactive waste. Many of these tanks and their associated infrastructure (e.g., pipelines, diversion boxes) have leaked. Some of the leaked waste has entered the groundwater. The largest known leak occurred from the T-106 Tank in 1973. Many of the contaminants from that leak still reside within the vadose zone beneath the T Tank Farm. CH2M Hill Hanford Group, Inc. seeks to minimize movement of this residual contaminant plume by placing an interim barrier on the surface. Such a barrier is expected to prevent infiltrating water from reaching the plume and moving it further. A plan has been prepared to monitor and determine the effectiveness of the interim surface barrier. Soil water content and water pressure will be monitored using off-the-shelf equipment that can be installed by the hydraulic hammer technique. In fiscal year 2006, two instrument nests were installed. Each instrument nest contains a neutron probe access tube, a capacitance probe, four heat-dissipation units, and a drain gauge to measure soil water flux. A meteorological station has been installed outside of the fence. In fiscal year 2007, two additional instrument nests are planned to be installed beneath the proposed barrier.

  16. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.

    2015-10-08

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  17. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.; Mudiyanselage, Kumudu; Burrell, Anthony K; Sadowski, Jerzy T.; Idriss, Hicham

    2015-01-01

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  18. Adiabatic flame temperature of sodium combustion and sodium-water reaction

    International Nuclear Information System (INIS)

    Okano, Y.; Yamaguchi, A.

    2001-01-01

    In this paper, background information of sodium fire and sodium-water reaction accidents of LMFBR (liquid metal fast breeder reactor) is mentioned at first. Next, numerical analysis method of GENESYS is described in detail. Next, adiabatic flame temperature and composition of sodium combustion are analyzed, and affect of reactant composition, such oxygen and moisture, is discussed. Finally, adiabatic reaction zone temperature and composition of sodium-water reaction are calculated, and affects of reactant composition, sodium vaporization, and pressure are stated. Chemical equilibrium calculation program for generic chemical system (GENESYS) is developed in this study for the research on adiabatic flame temperature of sodium combustion and adiabatic reaction zone temperature of sodium-water reaction. The maximum flame temperature of the sodium combustion is 1,950 K at the standard atmospheric condition, and is not affected by the existence of moisture. The main reaction product is Na 2 O (l) , and in combustion in moist air, with NaOH (g) . The maximum reaction zone temperature of the sodium-water reaction is 1,600 K, and increases with the system pressure. The main products are NaOH (g) , NaOH (l) and H2 (g) . Sodium evaporation should be considered in the cases of sodium-rich and high pressure above 10 bar

  19. Surface Intermediate Zone of Submerged Turbulent Buoyant Jet in Current

    DEFF Research Database (Denmark)

    Chen, H. B.; Larsen, Torben

    1995-01-01

    This paper deals with the intermediate zone between the jet and plume stages of a submerged buoyant discharge from sea outfall in current. The stability criteria, plume width and height after the intermediate zone and the dilution within the intermediate region have been studied theoretically and...

  20. Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

    Energy Technology Data Exchange (ETDEWEB)

    Tan Zuxian [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Yang Yifu [Department of Chemistry, Wuhan University, Wuhan 430072 (China)]. E-mail: yang-y-f1@vip.sina.com; Jiang Fengshan [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Shao Huixia [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2006-10-05

    A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I {sub tip}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I {sub sub}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected.

  1. Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Zuxian; Yang, Yifu; Jiang, Fengshan; Shao, Huixia [Wuhan University, Wuhan (China). Department of Chemistry

    2006-10-05

    A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I{sub tip}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I{sub sub}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected. (author)

  2. "Cleaning" the Surface of Hydroxyapatite Nanorods by a Reaction-Dissolution Approach.

    Science.gov (United States)

    Cao, Binrui; Yang, Mingying; Wang, Lin; Xu, Hong; Zhu, Ye; Mao, Chuanbin

    2015-10-21

    Synthetic nanoparticles are always terminated with coating molecules, which are often cytotoxic and not desired in biomedicine. Here we propose a novel reaction-dissolution approach to remove the cytotoxic coating molecules. A two-component solution is added to the nanoparticle solution; one component reacts with the coating molecules to form a salt whereas another is a solvent for dissolving and thus removing the salt. As a proof of concept, this work uses a NaOH-ethanol solution to remove the cytotoxic linoleic acid molecules coated on the hydroxyapatite nanorods (HAP-NRs). The removal of the coating molecules not only significantly improves the biocompatibility of HAP-NRs but also enables their oriented attachment into tightly-bound superstructures, which mimic the organized HAP crystals in bone and enamel and can promote the osteogenic differentiation of mesenchymal stem cells. Our reaction-dissolution approach can be extended to the surface "cleaning" of other nanomaterials.

  3. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

  4. Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

    2014-01-01

    Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

  5. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  6. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  7. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    Science.gov (United States)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  8. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  9. Small water/steam leaks in sodium heated steam generators: Evaluation of the reaction zone - effects on 2 1/4 Cr 1 Mo structural material

    International Nuclear Information System (INIS)

    Dumm, K.

    1975-01-01

    On the basis of experimental data the geometry of a small leak reaction zone can be predicted for given leak sizes and steam generator operation conditions. The effects of small leaks on 2 1/4 Cr 1 Mo material have been studied and completed with test results from foreign investigators. The results have to be considered as preliminary ones which have to be further qualified by additional information. (author)

  10. Small water/steam leaks in sodium heated steam generators: Evaluation of the reaction zone - effects on 2 1/4 Cr 1 Mo structural material

    Energy Technology Data Exchange (ETDEWEB)

    Dumm, K

    1975-07-01

    On the basis of experimental data the geometry of a small leak reaction zone can be predicted for given leak sizes and steam generator operation conditions. The effects of small leaks on 2 1/4 Cr 1 Mo material have been studied and completed with test results from foreign investigators. The results have to be considered as preliminary ones which have to be further qualified by additional information. (author)

  11. Photocatalytic surface reactions on indoor wall paint.

    Science.gov (United States)

    Salthammer, T; Fuhrmann, F

    2007-09-15

    The reduction of indoor air pollutants by air cleaning systems has received considerable interest, and a number of techniques are now available. So far, the method of photocatalysis was mainly applied by use of titanium dioxide (TiO2) in flow reactors under UV light of high intensity. Nowadays, indoor wall paints are equipped with modified TiO2 to work as a catalyst under indoor daylight or artificial light. In chamber experiments carried out under indoor related conditions itwas shown thatthe method works for nitrogen dioxide with air exchange and for formaldehyde without air exchange at high concentrations. In further experiments with volatile organic compounds (VOCs), a small effect was found for terpenoids with high kOH rate constants. For other VOCs and carbon monoxide there was no degradation at all or the surface acted as a reversible sink. Secondary emissions from the reaction of paint constituents were observed on exposure to light. From the results it is concluded that recipes of photocatalytic wall paints need to be optimized for better efficiency under indoor conditions.

  12. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  13. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  14. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L S; Kenny, M J; Wieczorek, L [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1994-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  15. On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

    Science.gov (United States)

    Resende, S F; Oliveira, B S; Augusti, R

    2018-06-21

    On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

  16. Application of a hybrid multiscale approach to simulate hydrologic and biogeochemical processes in the river-groundwater interaction zone.

    Energy Technology Data Exchange (ETDEWEB)

    Hammond, Glenn Edward; Yang, Xiaofan; Song, Xuehang; Song, Hyun-Seob; Hou, Zhangshuan; Chen, Xingyuan; Liu, Yuanyuan; Scheibe, Tim

    2017-03-01

    The groundwater-surface water interaction zone (GSIZ) plays an important role in riverine and watershed ecosystems as the exchange of waters of variable composition and temperature (hydrologic exchange flows) stimulate microbial activity and associated biogeochemical reactions. Variable temporal and spatial scales of hydrologic exchange flows, heterogeneity of the subsurface environment, and complexity of biogeochemical reaction networks in the GSIZ present challenges to incorporation of fundamental process representations and model parameterization across a range of spatial scales (e.g. from pore-scale to field scale). This paper presents a novel hybrid multiscale simulation approach that couples hydrologic-biogeochemical (HBGC) processes between two distinct length scales of interest.

  17. Competing reactions of selected atmospheric gases on Fe3O4 nanoparticles surfaces.

    Science.gov (United States)

    Eltouny, N; Ariya, Parisa A

    2014-11-14

    Heterogeneous reactions on atmospheric aerosol surfaces are increasingly considered important in understanding aerosol-cloud nucleation and climate change. To understand potential reactions in polluted atmospheres, the co-adsorption of NO2 and toluene to magnetite (Fe3O4i.e. FeO·Fe2O3) nanoparticles at ambient conditions was investigated for the first time. The surface area, size distribution, and morphology of Fe3O4 nanoparticles were characterized by BET method and high-resolution transmission electron microscopy. Adsorption isotherms, collected by gas chromatography with flame ionization detection, showed that the presence of NO2 decreased the adsorption of toluene. The analyses of the surface chemical composition of Fe3O4 by X-ray photoelectron spectroscopy (XPS) reveal that, upon the addition of NO2, the surface is oxidized and a contribution at 532.5 ± 0.4 eV in the O1s spectrum appears, showing that NO2 likely competes with toluene by dissociating on Fe(2+) sites and forming NO3(-). Different competing effects were observed for oxidized Fe3O4; oxidation occurred when exposed solely to NO2, whereas, the mixture of toluene and NO2 resulted in a reduction of the surface i.e. increased Fe(2+)/Fe(3+). Analyses by time of flight secondary ion mass spectrometry further suggest toluene reacts with Fe(3+) sites forming oxygenated organics. Our results indicate that on reduced magnetite, NO2 is more reactive and competes with toluene; in contrast, on oxidized Fe3O4, toluene is more reactive. Because magnetite can assume a range of oxidation ratios in the environment, different competing interactions between pollutants like NO2 and toluene could influence atmospheric processes, namely, the formation of Fe(2+) and the formation of atmospheric oxidants.

  18. Photoreactive polymer brushes for high-density patterned surface derivatization using a Diels-Alder photoclick reaction.

    Science.gov (United States)

    Arumugam, Selvanathan; Orski, Sara V; Locklin, Jason; Popik, Vladimir V

    2012-01-11

    Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities. © 2011 American Chemical Society

  19. Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

    Science.gov (United States)

    Banks, Simon T; Clary, David C

    2009-01-14

    We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

  20. High-Power Laser Cutting of Steel Plates: Heat Affected Zone Analysis

    Directory of Open Access Journals (Sweden)

    Imed Miraoui

    2016-01-01

    Full Text Available The thermal effect of CO2 high-power laser cutting on cut surface of steel plates is investigated. The effect of the input laser cutting parameters on the melted zone depth (MZ, the heat affected zone depth (HAZ, and the microhardness beneath the cut surface is analyzed. A mathematical model is developed to relate the output process parameters to the input laser cutting parameters. Three input process parameters such as laser beam diameter, cutting speed, and laser power are investigated. Mathematical models for the melted zone and the heat affected zone depth are developed by using design of experiment approach (DOE. The results indicate that the input laser cutting parameters have major effect on melted zone, heat affected zone, and microhardness beneath cut surface. The MZ depth, the HAZ depth, and the microhardness beneath cut surface increase as laser power increases, but they decrease with increasing cutting speed. Laser beam diameter has a negligible effect on HAZ depth but it has a remarkable effect on MZ depth and HAZ microhardness. The melted zone depth and the heat affected zone depth can be reduced by increasing laser cutting speed and decreasing laser power and laser beam diameter.

  1. Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

    Science.gov (United States)

    Hudson, R.; Loeffler, M. J.; Gerakines, P.

    2017-12-01

    The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

  2. Peculiarities of radionuclide contamination of different Semipalatinsk nuclear test site (SNTS) zones

    International Nuclear Information System (INIS)

    Kadyrzhanov, K.K.; Khazhekber, S.; Lukashenko, S.N.; Solodukhin, V.P.; Kazachevskij, I.V.; Poznyak, V.L.; Knyazev, B.B.; Rofer, Ch.

    2002-01-01

    The Semipalatinsk Nuclear Test Site occupies about 18500 km 2 . There are 3 basic test zones in this territory including various test platforms where different character nuclear explosions were carried out. On the test platforms of the 'Opytnoe Pole' zone air and ground tests were performed, including nuclear and hydronuclear (without nuclear reaction) explosions. On the other zones (the Degelen mountains and Balapan valley) the underground tests including camouflaged and excavation nuclear explosions were carried out. Each kind of these tests can be characterised by the quantity and composition of radionuclides which were formed during the nuclear explosion, by the area of their distribution, localisation of the radionuclides at various sites, radionuclide species in soil. Transfer of the products of the air and the ground nuclear explosions by air flows and their sedimentation on the ground surfaces have caused broadband radioactive plumes extending over hundreds of kilometres. As a result of hydronuclear experiments, plenty of alpha-active radionuclides, consisting of a nuclear device is thrown locally out. Besides the ground and the air explosions, radiation conditions of the territory of the SNTS were influenced by excavation explosions with ground throwing out. Such tests resulted in an intensive local pollution. Other zone of an original pollution is the Degelen mountains. Although an basic mass of the nuclear explosion products is obviously concentrated in basin cavities of the tunnels, the radionuclides are taken out on a day time surface together with waters acting in the basin cavity of the tunnels. The results of investigation of radionuclide pollution on the various platforms of the SNTS territory are presented. The results characterise the radionuclide pollution by specificity of spent tests

  3. Fault zone hydrogeology

    Science.gov (United States)

    Bense, V. F.; Gleeson, T.; Loveless, S. E.; Bour, O.; Scibek, J.

    2013-12-01

    Deformation along faults in the shallow crust (research effort of structural geologists and hydrogeologists. However, we find that these disciplines often use different methods with little interaction between them. In this review, we document the current multi-disciplinary understanding of fault zone hydrogeology. We discuss surface- and subsurface observations from diverse rock types from unlithified and lithified clastic sediments through to carbonate, crystalline, and volcanic rocks. For each rock type, we evaluate geological deformation mechanisms, hydrogeologic observations and conceptual models of fault zone hydrogeology. Outcrop observations indicate that fault zones commonly have a permeability structure suggesting they should act as complex conduit-barrier systems in which along-fault flow is encouraged and across-fault flow is impeded. Hydrogeological observations of fault zones reported in the literature show a broad qualitative agreement with outcrop-based conceptual models of fault zone hydrogeology. Nevertheless, the specific impact of a particular fault permeability structure on fault zone hydrogeology can only be assessed when the hydrogeological context of the fault zone is considered and not from outcrop observations alone. To gain a more integrated, comprehensive understanding of fault zone hydrogeology, we foresee numerous synergistic opportunities and challenges for the discipline of structural geology and hydrogeology to co-evolve and address remaining challenges by co-locating study areas, sharing approaches and fusing data, developing conceptual models from hydrogeologic data, numerical modeling, and training interdisciplinary scientists.

  4. Track treeing mechanism and plastic zone in solid Part 1: Initial development of plastic zone

    International Nuclear Information System (INIS)

    Li Boyang

    2008-01-01

    After neutron exposure and chemical etching in advance, latent tracks of recoil nucleon develop into pits on CR39 surface. During electrochemical etching, plastic zone is formed at top of pits. Some pits develop into tree cracks in the initial stage of plastic zone development. Physical and mathematical model of crack and plastic zone is proposed; parameter of development free path of plastic zone is presented. Based on integration of elementary theories the stress analysis is build up; based on analyses of measured parameters, a set of common relations between parameters is obtained. Integrate parameter analysis and stress analysis, depth of plastic zone development, law and phenomenon in experimental data can be interpreted completely

  5. Investigations of reactions between pure refractory metals and light gases with the field ion microscope and atom probe

    International Nuclear Information System (INIS)

    Krautz, E.; Haiml, G.

    1989-01-01

    The initial stages of selected reactions of the refractory metals tungsten, niobium and tantalum with hydrogen, oxygen, nitrogen and methane have been studied with the field ion microscope in atomic resolution whereby the composition of single net planes converages and surface zones could absolutely be analyzed with the atom probe by using field desorption under defined conditions at low temperatures. 14 refs., 9 figs. (Author)

  6. Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

    International Nuclear Information System (INIS)

    Zaera, F.; Somorhai, G.A.

    1985-01-01

    Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

  7. Spatio-Temporal Modelling of Dust Transport over Surface Mining Areas and Neighbouring Residential Zones

    Directory of Open Access Journals (Sweden)

    Eva Gulikova

    2008-06-01

    Full Text Available Projects focusing on spatio-temporal modelling of the living environment need to manage a wide range of terrain measurements, existing spatial data, time series, results of spatial analysis and inputs/outputs from numerical simulations. Thus, GISs are often used to manage data from remote sensors, to provide advanced spatial analysis and to integrate numerical models. In order to demonstrate the integration of spatial data, time series and methods in the framework of the GIS, we present a case study focused on the modelling of dust transport over a surface coal mining area, exploring spatial data from 3D laser scanners, GPS measurements, aerial images, time series of meteorological observations, inputs/outputs form numerical models and existing geographic resources. To achieve this, digital terrain models, layers including GPS thematic mapping, and scenes with simulation of wind flows are created to visualize and interpret coal dust transport over the mine area and a neighbouring residential zone. A temporary coal storage and sorting site, located near the residential zone, is one of the dominant sources of emissions. Using numerical simulations, the possible effects of wind flows are observed over the surface, modified by natural objects and man-made obstacles. The coal dust drifts with the wind in the direction of the residential zone and is partially deposited in this area. The simultaneous display of the digital map layers together with the location of the dominant emission source, wind flows and protected areas enables a risk assessment of the dust deposition in the area of interest to be performed. In order to obtain a more accurate simulation of wind flows over the temporary storage and sorting site, 3D laser scanning and GPS thematic mapping are used to create a more detailed digital terrain model. Thus, visualization of wind flows over the area of interest combined with 3D map layers enables the exploration of the processes of coal dust

  8. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  9. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method

    International Nuclear Information System (INIS)

    Chen, Jun; Sun, Zhigang; Zhang, Dong H.

    2015-01-01

    A three dimensional potential energy surface for the F + H 2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2) Q ] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H 2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface

  10. Dynamic loadings of sodium-water reactions in LMFBR and fusion power designs

    Energy Technology Data Exchange (ETDEWEB)

    Chan, C. K.

    1977-07-01

    In liquid metal fast breeder reactor and lithium cooled fusion reactor, a sodium loop is being proposed to transfer heat from the primary coolant loop to the steam turbine cycle. Although by careful design and quality assurance programs, the probability for steam generator tube failure can be minimized, failure will still occur. The direct contact of sodium and water would cause a chemical reaction where hydrogen and sodium compounds are produced. This paper presents an evaluation of the potential hazards as a result of such a reaction. An analytical method is developed to investigate the extent of the reaction zone and the propagation of the pressure wave in the sodium system. In the calculation, the chemical reaction is assumed to be instantaneous, governed by the equation 2Na(l)+H/sub 2/O(l)..-->..Na/sub 2/O(l)+H/sub 2/(g)+31.4 K cal/gm. mole. Both the temperature and pressure rise in the reaction zone can be established from the energy balance and the equation of state for the gaseous product. As a consequence of the energy released, the chemical products suddenly expand with a high velocity. The expansion also generates a shock wave in both the water and the sodium systems. Results indicate that the reaction zone can expand in a rate of 1500 ft/sec and a shock wave with initial strength of 2300 atmospheres propagates with a speed of 8000 ft/sec into the sodium system. The propagating characteristics of the shock wave are obtained by solving the basic fluid equations. The shock wave decays rapidly, in the neighborhood of milliseconds, as soon as the reaction zone stops to expand. The decrease in the reaction zone pressure allows more water to react with the sodium and a second pulse is generated.

  11. Dynamic loadings of sodium-water reactions in LMFBR and fusion power designs

    International Nuclear Information System (INIS)

    Chan, C.K.

    1977-01-01

    In liquid metal fast breeder reactor and lithium cooled fusion reactor, a sodium loop is being proposed to transfer heat from the primary coolant loop to the steam turbine cycle. Although by careful design and quality assurance programs, the probability for steam generator tube failure can be minimized, failure will still occur. The direct contact of sodium and water would cause a chemical reaction where hydrogen and sodium compounds are produced. This paper presents an evaluation of the potential hazards as a result of such a reaction. An analytical method is developed to investigate the extent of the reaction zone and the propagation of the pressure wave in the sodium system. In the calculation, the chemical reaction is assumed to be instantaneous, governed by the equation 2Na(l)+H 2 O(l)→Na 2 O(l)+H 2 (g)+31.4 K cal/gm. mole. Both the temperature and pressure rise in the reaction zone can be established from the energy balance and the equation of state for the gaseous product. As a consequence of the energy released, the chemical products suddenly expand with a high velocity. The expansion also generates a shock wave in both the water and the sodium systems. Results indicate that the reaction zone can expand in a rate of 1500 ft/sec and a shock wave with initial strength of 2300 atmospheres propagates with a speed of 8000 ft/sec into the sodium system. The propagating characteristics of the shock wave are obtained by solving the basic fluid equations. The shock wave decays rapidly, in the neighborhood of milliseconds, as soon as the reaction zone stops to expand. The decrease in the reaction zone pressure allows more water to react with the sodium and a second pulse is generated

  12. Electrochemically assisted organosol method for Pt-Sn nanoparticle synthesis and in situ deposition on graphite felt support: Extended reaction zone anodes for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lycke, Derek R.; Gyenge, Elod L. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2007-03-20

    Two electrochemically assisted variants of the Boenneman organosol method were developed for Pt-Sn nanoparticle synthesis and in situ deposition on graphite felt electrodes (e.g. thickness up to 2 mm). Tetraoctylammonium triethylhydroborate N(C{sub 8}H{sub 17}){sub 4}BH(C{sub 2}H{sub 5}){sub 3} was employed as colloid stabilizer and reductant dissolved in tetrahydrofuran (THF). The role of the electric field at a low deposition current density of 1.25 mA cm{sup -2} was mainly electrophoretic causing the migration and adsorption of N(C{sub 8}H{sub 17}){sub 4}BH(C{sub 2}H{sub 5}){sub 3} on the graphite felt surface where it reduced the PtCl{sub 2}-SnCl{sub 2} mixture. Faradaic electrodeposition was detected mostly for Sn. Typical Pt-Sn loadings were between 0.4 and 0.9 mg cm{sup -2} depending on the type of pre-deposition exposure of the graphite felt: surfactant-adsorption and metal-adsorption variant, respectively. The catalyst surface area and Pt:Sn surface area ratio was determined by anodic striping of an underpotential deposited Cu monolayer. The two deposition variants gave different catalyst surfaces: total area 233 and 76 cm{sup 2} mg{sup -1}, with Pt:Sn surface area ratio of 3.5:1 and 7.7:1 for surfactant and metal adsorption, respectively. Regarding electrocatalysis of ethanol oxidation, voltammetry and chronopotentiometry studies corroborated by direct ethanol fuel cell experiments using 0.5 M H{sub 2}SO{sub 4} as electrolyte, showed that due to a combination of higher catalyst load and Pt:Sn surface ratio, the graphite felt anodes prepared by the metal-adsorption variant gave better performance. The catalyzed graphite felt provided an extended reaction zone for ethanol electrooxidation and it gave higher catalyst mass specific peak power outputs compared to literature data obtained using gas diffusion anodes with carbon black supported Pt-Sn nanoparticles. (author)

  13. Driving Ability of HMX based Aluminized Explosive Affected by the Reaction Degree of Aluminum Powder

    Science.gov (United States)

    Duan, Yingliang

    2017-06-01

    Due to the time scale of aluminum reaction, the detonation process of the aluminized explosive becomes very complex, and there is less agreement on the reaction mechanism of aluminum powder. If the reaction of aluminum occurs in the reaction zone, the energy released will further strengthen the work ability of detonation wave. So it is very important for characterizing the detonation parameters and detonation driving ability to accurately understand the role of aluminum powder in the reaction zone. In this paper, detonation driving process of HMX based aluminized explosive was studied by cylinder test, obtaining the expansion track of cylinder wall. In order to further research the reaction degree (λ) of aluminum in the reaction zone, the thermodynamic program VHL was used to calculate the detonation process at different reaction degrees, obtaining the parameters of detonation products thermodynamic state. Using the dynamic software LS-DYNA and the JWL equation of state by fitting the pressure and relative volume relationship, the cylinder test was simulated. Compared with the experimental results, when the reaction degree is 20%, the driving ability is found to be in agreement with measured ones. It is concluded that the driving ability of HMX based aluminized explosive can be more accurately characterized by considering the reaction degree of aluminum powder in the reaction zone.

  14. Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer

    Energy Technology Data Exchange (ETDEWEB)

    Grenier, Antonin [X-ray; Liu, Hao [X-ray; Wiaderek, Kamila M. [X-ray; Lebens-Higgins, Zachary W. [Department; Borkiewicz, Olaf J. [X-ray; Piper, Louis F. J. [Department; Chupas, Peter J. [Energy; Chapman, Karena W. [X-ray

    2017-08-15

    Through operando synchrotron powder X-ray diffraction (XRD) analysis of layered transition metal oxide electrodes of composition LiNi0.8Co0.15Al0.05O2 (NCA), we decouple the intrinsic bulk reaction mechanism from surface-induced effects. For identically prepared and cycled electrodes stored in different environments, we demonstrate that the intrinsic bulk reaction for pristine NCA follows solid-solution mechanism, not a two-phase as suggested previously. By combining high resolution powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and surface sensitive X-ray photoelectron spectroscopy (XPS), we demonstrate that adventitious Li2CO3 forms on the electrode particle surface during exposure to air, through reaction with atmospheric CO2. This surface impedes ionic and electronic transport to the underlying electrode, with progressive erosion of this layer during cycling giving rise to different reaction states in particles with an intact vs an eroded Li2CO3 surface-coating. This reaction heterogeneity, with a bimodal distribution of reaction states, has previously been interpreted as a “two-phase” reaction mechanism for NCA, as an activation step that only occurs during the first cycle. Similar surface layers may impact the reaction mechanism observed in other electrode materials using bulk probes such as operando powder XRD.

  15. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-04-20

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  16. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    International Nuclear Information System (INIS)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-01-01

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  17. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-03-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

  18. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    Science.gov (United States)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  19. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

    Science.gov (United States)

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  20. Slip Zone versus Damage Zone Micromechanics, Arima-Takasuki Tectonic Line, Japan

    Science.gov (United States)

    White, J. C.; Lin, A.

    2017-12-01

    The Arima-Takasuki Tectonic Line (ATTL) of southern Honshu, Japan is defined by historically active faults and multiple splays producing M7 earthquakes. The damage zone of the ATTL comprises a broad zone of crushed, comminuted and pulverized granite/rhyolite1,2containing cm-scale slip zones and highly comminuted injection veins. In this presentation, prior work on the ATTL fault rocks is extending to include microstructural characterization by transmission electron microscopy (TEM) from recent trenching of the primary slip zone, as well as secondary slip zones. This is necessary to adequately characterize the extremely fine-grained material (typically less than 1mm) in both damage and core zones. Damage zone material exhibits generally random textures3 whereas slip zones are macroscopically foliated, and compositionally layered, notwithstanding a fairly homogeneous protolith. The latter reflects fluid-rock interaction during both coseismic and interseismic periods. The slip zones are microstructurally heterogeneous at all scales, comprising not only cataclasites and phyllosilicate (clay)-rich gouge zones, but Fe/Mn pellets or clasts that are contained within gouge. These structures appear to have rolled and would suggest rapid recrystallization and/or growth. A central question related to earthquake recurrence along existing faults is the nature of the gouge. In both near-surface exposures and ongoing drilling at depth, "plastic" or "viscous" gouge zones comprise ultra-fine-grained clay-siliciclastic particles that would not necessarily respond in a simple frictional manner. Depending on whether the plastic nature of these slip zones develops during or after slip, subsequent focusing of slip within them could be complicated. 1 Mitchell, T.A., Ben-Zion, Y., Shimamoto, T., 2011. Ear. Planet. Sci. Lett. 308, 284-297. 2 Lin, A., Yamashita, K, Tanaka, M. J., 2013. Struc. Geol. 48, 3-13. 3 White, J.C., Lin, A. 2016. Proc. AGU Fall Mtg., T42-02 San Francisco.

  1. Land Surface Temperature Differences within Local Climate Zones, Based on Two Central European Cities

    Czech Academy of Sciences Publication Activity Database

    Geletič, Jan; Lehnert, M.; Dobrovolný, Petr

    2016-01-01

    Roč. 8, č. 10 (2016), č. článku 788. ISSN 2072-4292 R&D Projects: GA MŠk(CZ) LO1415 Grant - others:UrbanAdapt(XE) EHP-CZ02-OV-1-036-2015 Program:CZ02 Biodiverzita a ekosystémové služby / Monitorování a integrované plánování a kontrola v životním prostředí/ Adaptace na změnu klimatu Institutional support: RVO:67179843 Keywords : land surface temperature * local climate zones * ASTER * LANDSAT * analysis of variance * Prague * Brno * Czech Republic Subject RIV: EH - Ecology, Behaviour Impact factor: 3.244, year: 2016

  2. The Biomantle-Critical Zone Model

    Science.gov (United States)

    Johnson, D. L.; Lin, H.

    2006-12-01

    It is a fact that established fields, like geomorphology, soil science, and pedology, which treat near surface and surface processes, are undergoing conceptual changes. Disciplinary self examinations are rife. New practitioners are joining these fields, bringing novel and interdisciplinary ideas. Such new names as "Earth's critical zone," "near surface geophysics," and "weathering engine" are being coined for research groups. Their agendas reflect an effort to integrate and reenergize established fields and break new ground. The new discipline "hydropedology" integrates soil science with hydrologic principles, and recent biodynamic investigations have spawned "biomantle" concepts and principles. One force behind these sea shifts may be retrospectives whereby disciplines periodically re-invent themselves to meet new challenges. Such retrospectives may be manifest in the recent Science issue on "Soils, The Final Frontier" (11 June, 2004), and in recent National Research Council reports that have set challenges to science for the next three decades (Basic Research Opportunities in Earth Science, and Grand Challenges for the Environmental Sciences, both published in 2001). In keeping with such changes, we advocate the integration of biomantle and critical zone concepts into a general model of Earth's soil. (The scope of the model automatically includes the domain of hydropedology.) Our justification is that the integration makes for a more appealing holistic, and realistic, model for the domain of Earth's soil at any scale. The focus is on the biodynamics of the biomantle and water flow within the critical zone. In this general model the biomantle is the epidermis of the critical zone, which extends to the base of the aquifer. We define soil as the outer layer of landforms on planets and similar bodies altered by biological, chemical, and/or physical agents. Because Earth is the only planet with biological agents, as far as we know, it is the only one that has all

  3. Optimization of Al-CVD process based on elementary reaction simulation and experimental verification: From the growth rate to the surface morphology

    International Nuclear Information System (INIS)

    Sugiyama, Masakazu; Iino, Tomohisa; Nakajima, Tohru; Tanaka, Takeshi; Egashira, Yasuyuki; Yamashita, Kohichi; Komiyama, Hiroshi; Shimogaki, Yukihiro

    2006-01-01

    We propose a method to reduce the surface roughness of Al film in the chemical vapor deposition (CVD) using dimethyl-aluminum-hydride (DMAH) as the precursor. An elementary reaction simulation was executed not only to predict the deposition rate but also to predict the coverage of the film by surface adsorbates. It was assumed that high surface coverage is essential in order to deposit smooth films because the adsorbates protect the surface from oxidation which causes discontinuous growth of crystal grains. According to this principle, the condition, that realizes both high surface coverage and high deposition rate at the same time by using the elementary reaction simulation, was sought. A nozzle inlet was used instead of a conventional showerhead. This drastically improved the surface morphology, showing the effectiveness of this theoretical optimization procedure

  4. HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

    International Nuclear Information System (INIS)

    Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

    2004-01-01

    We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

  5. Mass Transfer Limited Enhanced Bioremediation at Dnapl Source Zones: a Numerical Study

    Science.gov (United States)

    Kokkinaki, A.; Sleep, B. E.

    2011-12-01

    The success of enhanced bioremediation of dense non-aqueous phase liquids (DNAPLs) relies on accelerating contaminant mass transfer from the organic to the aqueous phase, thus enhancing the depletion of DNAPL source zones compared to natural dissolution. This is achieved by promoting biological activity that reduces the contaminant's aqueous phase concentration. Although laboratory studies have demonstrated that high reaction rates are attainable by specialized microbial cultures in DNAPL source zones, field applications of the technology report lower reaction rates and prolonged remediation times. One possible explanation for this phenomenon is that the reaction rates are limited by the rate at which the contaminant partitions from the DNAPL to the aqueous phase. In such cases, slow mass transfer to the aqueous phase reduces the bioavailability of the contaminant and consequently decreases the potential source zone depletion enhancement. In this work, the effect of rate limited mass transfer on bio-enhanced dissolution of DNAPL chlorinated ethenes is investigated through a numerical study. A multi-phase, multi-component groundwater transport model is employed to simulate DNAPL mass depletion for a range of source zone scenarios. Rate limited mass transfer is modeled by a linear driving force model, employing a thermodynamic approach for the calculation of the DNAPL - water interfacial area. Metabolic reductive dechlorination is modeled by Monod kinetics, considering microbial growth and self-inhibition. The model was utilized to identify conditions in which mass transfer, rather than reaction, is the limiting process, as indicated by the bioavailability number. In such cases, reaction is slower than expected, and further increase in the reaction rate does not enhance mass depletion. Mass transfer rate limitations were shown to affect both dechlorination and microbial growth kinetics. The complex dynamics between mass transfer, DNAPL transport and distribution, and

  6. Facile synthesis of graphene on dielectric surfaces using a two-temperature reactor CVD system

    International Nuclear Information System (INIS)

    Zhang, C; Man, B Y; Yang, C; Jiang, S Z; Liu, M; Chen, C S; Xu, S C; Sun, Z C; Gao, X G; Chen, X J

    2013-01-01

    Direct deposition of graphene on a dielectric substrate is demonstrated using a chemical vapor deposition system with a two-temperature reactor. The two-temperature reactor is utilized to offer sufficient, well-proportioned floating Cu atoms and to provide a temperature gradient for facile synthesis of graphene on dielectric surfaces. The evaporated Cu atoms catalyze the reaction in the presented method. C atoms and Cu atoms respectively act as the nuclei for forming graphene film in the low-temperature zone and the zones close to the high-temperature zones. A uniform and high-quality graphene film is formed in an atmosphere of sufficient and well-proportioned floating Cu atoms. Raman spectroscopy, scanning electron microscopy and atomic force microscopy confirm the presence of uniform and high-quality graphene. (paper)

  7. CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

    Science.gov (United States)

    Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

    2002-01-01

    Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

  8. Making the most of CZ seismics: Improving shallow critical zone characterization using surface-wave analysis

    Science.gov (United States)

    Pasquet, S.; Wang, W.; Holbrook, W. S.; Bodet, L.; Carr, B.; Flinchum, B. A.

    2017-12-01

    Estimating porosity and saturation in the shallow subsurface over large lateral scales is vitally important for understanding the development and evolution of the Critical Zone (CZ). Because elastic properties (P- and S-wave velocities) are particularly sensitive to porosity and saturation, seismic methods (in combination with petrophysical models) are effective tools for mapping CZ architecture and processes. While many studies employ P-wave refraction methods, fewer use the surface waves that are typically also recorded in those same surveys. Here we show the value of exploiting surface waves to extract supplementary shear-wave velocity (Vs) information in the CZ. We use a new, user-friendly, open-source MATLAB-based package (SWIP) to invert surface-wave data and estimate lateral variations of Vs in the CZ. Results from synthetics show that this approach enables the resolution of physical property variations in the upper 10-15 m below the surface with lateral scales of about 5 m - a vast improvement compared to P-wave tomography alone. A field example at a Yellowstone hydrothermal system also demonstrates the benefits of including Vs in the petrophysical models to estimate not only porosity but also saturation, thus highlighting subsurface gas pathways. In light of these results, we strongly suggest that surface-wave analysis should become a standard approach in CZ seismic surveys.

  9. Effect of surface reaction layer on grindability of cast titanium alloys.

    Science.gov (United States)

    Ohkubo, Chikahiro; Hosoi, Toshio; Ford, J Phillip; Watanabe, Ikuya

    2006-03-01

    The purpose of this study was to investigate the effect of the cast surface reaction layer on the grindability of titanium alloys, including free-machining titanium alloy (DT2F), and to compare the results with the grindability of two dental casting alloys (gold and Co-Cr). All titanium specimens (pure Ti, Ti-6Al-4V and DT2F) were cast using a centrifugal casting machine in magnesia-based investment molds. Two specimen sizes were used to cast the titanium metals so that the larger castings would be the same size as the smaller gold and Co-Cr alloy specimens after removal of the surface reaction layer (alpha-case). Grindability was measured as volume loss ground from a specimen for 1 min using a handpiece engine with a SiC abrasive wheel at 0.1 kgf and four circumferential wheel speeds. For the titanium and gold alloys, grindability increased as the rotational speed increased. There was no statistical difference (p>0.05) in grindability for all titanium specimens either with or without the alpha-case. Of the titanium metals tested, Ti-6 Al-4V had the greatest grindability at higher speeds, followed by DT2F and CP Ti. The grindability of the gold alloy was similar to that of Ti-6 Al-4V, whereas the Co-Cr alloy had the lowest grindability. The results of this study indicated that the alpha-case did not significantly affect the grindability of the titanium alloys. The free-machining titanium alloy had improved grindability compared to CP Ti.

  10. Two dimensional simulation of hydrogen iodide decomposition reaction using fluent code for hydrogen production using nuclear technology

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Jung Sik [The Institute of Machinery and Electronic Technology, Mokpo National Maritime University, Mokpo (Korea, Republic of); Shin, Young Joon; Lee, Ki Young [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Jae Hyuk [Division of Marine Engineering System, Korea Maritime and Ocean University, Busan (Korea, Republic of)

    2015-06-15

    The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen production were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribution, were studied to compare device performance with that expected for device development. Hydrogen production increased with an increase of the surface-to-volume (STV) ratio. With an increase of hydrogen production, the reaction heat increased. The internal pressure and velocity of the HI decomposer were estimated through pressure drop and reducing velocity from the preheating zone. The mass of H2O was independent of the STV ratio, whereas that of HI decreased with increasing STV ratio.

  11. Synthesis, surface properties and antimicrobial activity of some germanium nonionic surfactants.

    Science.gov (United States)

    Zaki, Mohamed F; Tawfik, Salah M

    2014-01-01

    Esterification reaction between different fatty acid namely; lauric, stearic, oleic and linoleic acids and polyethylene glycol-400 were performed. The produced polyethylene glycol ester were reacted with p-amine benzoic acid followed by condensation reaction with germanium dioxide in presence of sodium carbonate to form desired germinate surfactants. The chemical structures of the synthesized surfactants were determined using different spectra tools. The surface parameter including: the critical micelle concentration (CMC), effectiveness (π(cmc)), efficiency (Pc20), maximum surface excess (Γ(max)) and minimum surface area (A(min)), were calculated from the surface tension measurements. The synthesized surfactants showed higher surface activity. The thermodynamic parameters showed that adsorption and micellization processes are spontaneous. It is clear that the synthesized nonionic surfactants showed their tendency towards adsorption at the interfaces and also micellization in the bulk of their solutions. The synthesized surfactants were tested against different strain of bacteria using inhibition zone diameters. The synthesized surfactants showed good antimicrobial activities against the tested microorganisms including Gram positive, Gram negative as well as fungi. The promising inhibition efficiency of these compounds against the sulfate reducing bacteria facilitates them to be applicable as new categories of sulfate reducing bacteria biocides.

  12. An accurate potential energy surface for the F + H{sub 2} → HF + H reaction by the coupled-cluster method

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jun; Sun, Zhigang, E-mail: zsun@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: zsun@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2015-01-14

    A three dimensional potential energy surface for the F + H{sub 2} → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2){sub Q}] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H{sub 2} reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

  13. DNAPL Surface Chemistry: Its Impact on DNAPL Distribution in the Vadose Zone and its Manipulation to Enhance Remediation

    Energy Technology Data Exchange (ETDEWEB)

    Suan Power; Stefan Grimberg; Miles Denham

    2003-06-16

    The remediation of DNAPLs in subsurface environments is often limited by the heterogeneous distribution of the organic fluid. The fraction of DNAPL that is in the high conductivity regions of the subsurface can often be recovered relatively easily, although DNAPL in lower conductivity regions is much more difficult to extract, either through direct pumping or remediation measures based on interface mass transfer. The distribution of DNAPL within the vadose zone is affected by a complex interplay of heterogeneities in the porous matrix and the interfacial properties defining the interactions among all fluid and solid phases. Decreasing the interfacial tension between a DNAPL and water in the vadose zone could change the spreading of the DNAPL, thereby increase the surface area for mass transfer and the effectiveness of soil vapor extraction remediation.

  14. Potential surfaces in symmetric heavy-ion reactions

    International Nuclear Information System (INIS)

    Royer, G.; Piller, C.; Mignen, J.; Raffray, Y.

    1989-01-01

    The entrance channel in symmetric heavy-ion reactions is studied in the liquid-drop model approach including the nuclear proximity energy and allowing ellipsoidal deformations of the colliding nuclei. In the whole mass range a sudden transition occurs from oblate to prolate shapes when the proximity forces become important. This strongly affects the effective moment of inertia. The ellipsoidal deformations reduce the fusion barrier width for light systems and lower the potential barrier height for medium and heavy nuclei. The results are in agreement with the empirical effective barrier shift determined by Aguiar et al for the 58 Ni + 58 Ni, 74 Ge + 74 Ge and 80 Se + 80 Se systems. The sub-barrier fusion enhancement in heavy-ion reactions might be explained by the slowness of the process. Below the static fusion barrier, the reaction time is long; allowing some adiabaticity and deformations of the colliding ions. Above the barrier, the reaction is more sudden and the deformation degree of freedom is frozen

  15. Molecular dynamics simulation of sodium aluminosilicate glass structures and glass surface-water reactions using the reactive force field (ReaxFF)

    Science.gov (United States)

    Dongol, R.; Wang, L.; Cormack, A. N.; Sundaram, S. K.

    2018-05-01

    Reactive potentials are increasingly used to study the properties of glasses and glass water reactions in a reactive molecular dynamics (MD) framework. In this study, we have simulated a ternary sodium aluminosilicate glass and investigated the initial stages of the glass surface-water reactions at 300 K using reactive force field (ReaxFF). On comparison of the simulated glass structures generated using ReaxFF and classical Buckingham potentials, our results show that the atomic density profiles calculated for the surface glass structures indicate a bond-angle distribution dependency. The atomic density profiles also show higher concentrations of non-bridging oxygens (NBOs) and sodium ions at the glass surface. Additionally, we present our results of formation of silanol species and the diffusion of water molecules at the glass surface using ReaxFF.

  16. Arsenic transport in groundwater, surface water, and the hyporheic zone of a mine-influenced stream-aquifer system

    OpenAIRE

    Brown, Brendan

    2005-01-01

    We investigated the transport of dissolved arsenic in groundwater, surface water and the hyporheic zone in a stream-aquifer system influenced by an abandoned arsenopyrite mine. Mine tailing piles consisting of a host of arsenic-bearing minerals including arsenopyrite and scorodite remain adjacent to the stream and represent a continuous source of arsenic. Arsenic loads from the stream, springs, and groundwater were quantified at the study reach on nine dates from January to August 2005 and ...

  17. A global model for SF6 plasmas coupling reaction kinetics in the gas phase and on the surface of the reactor walls

    International Nuclear Information System (INIS)

    Kokkoris, George; Panagiotopoulos, Apostolos; Gogolides, Evangelos; Goodyear, Andy; Cooke, Mike

    2009-01-01

    Gas phase and reactor wall-surface kinetics are coupled in a global model for SF 6 plasmas. A complete set of gas phase and surface reactions is formulated. The rate coefficients of the electron impact reactions are based on pertinent cross section data from the literature, which are integrated over a Druyvesteyn electron energy distribution function. The rate coefficients of the surface reactions are adjustable parameters and are calculated by fitting the model to experimental data from an inductively coupled plasma reactor, i.e. F atom density and pressure change after the ignition of the discharge. The model predicts that SF 6 , F, F 2 and SF 4 are the dominant neutral species while SF 5 + and F - are the dominant ions. The fit sheds light on the interaction between the gas phase and the reactor walls. A loss mechanism for SF x radicals by deposition of a fluoro-sulfur film on the reactor walls is needed to predict the experimental data. It is found that there is a net production of SF 5 , F 2 and SF 6 , and a net consumption of F, SF 3 and SF 4 on the reactor walls. Surface reactions as well as reactions between neutral species in the gas phase are found to be important sources and sinks of the neutral species.

  18. Reaction of [3H]-taurine maleimide with platelet surface thiols

    International Nuclear Information System (INIS)

    Karl, D.W.; Mills, D.C.B.

    1986-01-01

    Taurine Maleimide (2-maleimidoethanesulfonate, TM) was synthesized from [2- 3 H]-taurine and methoxycarbonylmaleimide (MCM). The yield of a 1 μmol synthesis approached 100% (based on taurine) when MCM was used in 4-fold excess. The product (TM*) was purified by ion exchange chromatography. TM* reacted irreversibly with thiol groups on the surface of washed human platelets, leading to incorporation of radioactivity into platelet pellets. Incorporation was blocked by cysteine, mercuribenzenesulfonate (MBS), dithiobisnitrobenzoate, and N-ethylmaleimide, but not by taurine or by inhibitors of anion transport. Reaction of TM* with platelets showed the dependence on time and concentration characteristics of a bimolecular reaction. The number of reactive sites ranged from 1 to 5 x 10 5 /platelet, and the apparent rate constant from 1 to 3 x 10 3 /(M x min). TM was less effective than MBS as an inhibitor of platelet aggregation induced by several agents. TM had no effect on the uptake of serotonin, taurine, or phosphate by the platelets, processes which are sensitive to MBS. These differences, considered with the similarity in size and charge of TM and MBS, suggest that classes of thiols defined as exofacial by their accessibility to MBS can differ substantially in their reactivity with other impermeant reagents

  19. Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

    Science.gov (United States)

    Rissmann, C.; Christenson, B.; Werner, C.; Leybourne, M.; Cole, J.; Gravley, D.

    2012-01-01

    Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20a of production (116MW e). Soil CO2 degassing was quantified with 2663 CO2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (Wm -2) using published soil temperature heat flow functions. Both CO2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20a of production, current CO2 emissions equated to 111??6.7T/d. Observed heat flow was 70??6.4MW, compared with a pre-production value of 122MW. This 52MW reduction in surface heat flow is due to production-induced drying up of all alkali-Cl outflows (61.5MW) and steam-heated pools (8.6MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali-Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18MW (from 25MW to 43.3??5MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20a of production, with an observed heat flow of 26.7??3MW and a CO 2 emission rate of 39??3T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali-Cl outflows once contributed significantly to the natural surface heat flow (~50%) they contributed little (99% of the original CO 2

  20. Local Effects of Ice Floes on Skin Sea Surface Temperature in the Marginal Ice Zone from UAVs

    Science.gov (United States)

    Zappa, C. J.; Brown, S.; Emery, W. J.; Adler, J.; Wick, G. A.; Steele, M.; Palo, S. E.; Walker, G.; Maslanik, J. A.

    2013-12-01

    Recent years have seen extreme changes in the Arctic. Particularly striking are changes within the Pacific sector of the Arctic Ocean, and especially in the seas north of the Alaskan coast. These areas have experienced record warming, reduced sea ice extent, and loss of ice in areas that had been ice-covered throughout human memory. Even the oldest and thickest ice types have failed to survive through the summer melt period in areas such as the Beaufort Sea and Canada Basin, and fundamental changes in ocean conditions such as earlier phytoplankton blooms may be underway. Marginal ice zones (MIZ), or areas where the "ice-albedo feedback" driven by solar warming is highest and ice melt is extensive, may provide insights into the extent of these changes. Airborne remote sensing, in particular InfraRed (IR), offers a unique opportunity to observe physical processes at sea-ice margins. It permits monitoring the ice extent and coverage, as well as the ice and ocean temperature variability. It can also be used for derivation of surface flow field allowing investigation of turbulence and mixing at the ice-ocean interface. Here, we present measurements of visible and IR imagery of melting ice floes in the marginal ice zone north of Oliktok Point AK in the Beaufort Sea made during the Marginal Ice Zone Ocean and Ice Observations and Processes EXperiment (MIZOPEX) in July-August 2013. The visible and IR imagery were taken from the unmanned airborne vehicle (UAV) ScanEagle. The visible imagery clearly defines the scale of the ice floes. The IR imagery show distinct cooling of the skin sea surface temperature (SST) as well as a intricate circulation and mixing pattern that depends on the surface current, wind speed, and near-surface vertical temperature/salinity structure. Individual ice floes develop turbulent wakes as they drift and cause transient mixing of an influx of colder surface (fresh) melt water. The upstream side of the ice floe shows the coldest skin SST, and

  1. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  2. Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

    Science.gov (United States)

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2009-12-02

    Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

  3. Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

    Science.gov (United States)

    Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

    2017-03-01

    The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

  4. A geophysical cross-section of the Hockai Fault Zone (Eastern Belgium): imaging an intraplate weak crustal zone.

    Science.gov (United States)

    Lecocq, T.; Camelbeeck, T.

    2016-12-01

    The Hockai Fault Zone (HFZ) is a NNW-SSE trending structure visible in the regional geomorphology in the Ardennes, Eastern-Belgium. It is situated, between the Pays de Herve (Graben de la Minerie) to the North and the Amblève river, to the South. It crosses the Stavelot Massif, almost perpendicular to the Crête de la Vecquée (Vecquée crest), i.e. the highest crest of the Venn. Faults have been identified or suspected on a contour map of the base of the Tertiary cover (Eocene or Oligocene) in the north western and central Rhenish Massif. These faults are necessary to account for the altitude difference of the base of the cover. The deflection or capture of local rivers show a remarkable alignments on more than 42 km N-S. The alignments are mostly trending SSE-NNW, between N140 and N170, with some potential segments with slightly different orientations. This general orientation has been also evidenced from the analyses of Landsat-1 imagery products. At its crossing with the Vecquée Crest, Demoulin locates the HFZ where the Hoëgne river turns sharply towards the north and crosscuts the quarzitic crest. Demoulin identifies three subparallel faults or fault zones on the Hautes-Fagnes plateau, from East to West: the Eupen faulting zone, the Baelen faulting zone and Hockai faulted zone. In this communication, we report on a large-scale geophysical survey that was conducted in order to search of the Hockai fault zone expression at the surface. The locations to search for the Hockai Fault Zone are based on the surface projection of the 1989/1990 seismic swarm that occurred under the Stavelot Massif, geomorphological evidences and past geophysical surveys in the region. Our objective is not to prove a Quaternary movement of faults, but rather to find reliable evidences of their presence and to analyse their lateral extension. In total, 31 ERT profiles were executed almost parallel to the Vecquée Crest, i.e. a total of 10679 meters of profiles. Four zones are imaged

  5. Proton magnetic spectroscopy agreed better with magnetic resonance image to lateralization of epileptogenic zone than with surface electroencephalography

    Directory of Open Access Journals (Sweden)

    Ricardo Andre Amorim Leite

    2013-09-01

    Full Text Available Objective To analyze the agreement rate of proton magnetic spectroscopy with magnetic resonance image (MRI and surface electroence-phalography (EEG in extratemporal neocortical epilepsies. Methods A cross-sectional study, type series of cases included 33 patients, age range 13–59 years old, of both gender, presenting structural alteration identified by MRI (75.8% or by neurophysiologic techniques (72.7%. The variables were alterations of N-acetyl-aspartate/choline, N-acetyl-aspartate/creatine, choline/creatine, and N-acetyl-aspartate/cho-line+creatine coefficient of asymmetry. Results Agreement rates of lateralization by coefficient of asymmetry of NAA/Cho, NAA/Cr, Co/Cr, and NAA/Cho+Cr with MRI, independent of alteration of surface EEG, were equal to 93.3, 57.9, 15.4, and 93.3%, respectively, modifying to 100, 33.3, 0, and 100%, in 16 patients, with lateralization agreement of MRI and surface EEG. Conclusion Proton magnetic spectroscopy agreed better with MRI to lateralization of epileptogenic zone than with surface EEG.

  6. Multi-pollutant interactions in hyporheic zones

    Science.gov (United States)

    Krause, S.; Weatherill, J.; Bonet, B.; Blaen, P.; Khamis, K.; Cassidy, N. J.; Hannah, D. M.; Rivett, M. O.; Lynch, I.; Ullah, S.

    2017-12-01

    Hyporheic zones represent hotspots of biogeochemical reactivity, with the potential to attenuate pollutants and ameliorate their impact on ecosystem functioning. Sources and types of pollutants in streambed environments are manifold, with legacy industry contaminants, agricultural pollution and emerging pollutants such as pharmaceuticals or engineered nanoparticles entering hyporheic zones along different flow paths where they mix and potentially react with each other. Current conceptualizations of drivers and controls of biogeochemical turnover in hyporheic zones highlight primarily the role of transport and reaction times but do not account for potential interactions between different pollutants. This study presents two case studies of multi-pollutant interactions to illustrate the need to consider interferences between different pollutants, their transport and reaction pathways for adequate impact assessment. We discuss in the first instance how the natural attenuation of a Trichloroethylene (TCE) groundwater plume in an agricultural catchment is limited by high riparian and hyporheic nitrate concentrations. As nitrate outcompeted TCE in its reaction with organic carbon as electron donor, TCE attenuation was in this case limited to hyporheic denitrification hotspots. Hence any pollution control measures to reduce the impact of this TCE plume require a reduction of agricultural nitrate loads, highlighting the connectedness of legacy (TCE) and more recent (nitrate) pollution problems. In the second case, we investigate how the labile organic carbon content of streambed sediments as main control of hyporheic respiration is overridden by exposure to different silver nanoparticle concentrations, representing emerging pollutants in many of our rivers. Also in this case, the impacts of different stressors (nanoparticle exposure) and drivers (availability of organic matter, water temperature) are interacting in their impacts on hyporheic zone functioning. We argue that

  7. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  8. Seismic Evidence of A Widely Distributed West Napa Fault Zone, Hendry Winery, Napa, California

    Science.gov (United States)

    Goldman, M.; Catchings, R.; Chan, J. H.; Criley, C.

    2015-12-01

    Following the 24 August 2014 Mw 6.0 South Napa earthquake, surface rupture was mapped along the West Napa Fault Zone (WNFZ) for a distance of ~ 14 km and locally within zones up to ~ 2 km wide. Near the northern end of the surface rupture, however, several strands coalesced to form a narrow, ~100-m-wide zone of surface rupture. To determine the location, width, and shallow (upper few hundred meters) geometry of the fault zone, we acquired an active-source seismic survey across the northern surface rupture in February 2015. We acquired both P- and S-wave data, from which we developed reflection images and tomographic images of Vp, Vs, Vp/Vs, and Poisson's ratio of the upper 100 m. We also used small explosive charges within surface ruptures located ~600 m north of our seismic array to record fault-zone guided waves. Our data indicate that at the latitude of the Hendry Winery, the WNFZ is characterized by at least five fault traces that are spaced 60 to 200 m apart. Zones of low-Vs, low-Vp/Vs, and disrupted reflectors highlight the fault traces on the tomography and reflection images. On peak-ground-velocity (PGV) plots, the most pronounced high-amplitude guided-wave seismic energy coincides precisely with the mapped surface ruptures, and the guided waves also show discrete high PGV zones associated with unmapped fault traces east of the surface ruptures. Although the surface ruptures of the WNFZ were observed only over a 100-m-wide zone at the Hendry Winery, our data indicate that the fault zone is at least 400 m wide, which is probably a minimum width given the 400-m length of our seismic profile. Slip on the WNFZ is generally considered to be low relative to most other Bay Area faults, but we suggest that the West Napa Fault is a zone of widely distributed shear, and to fully account for the total slip on the WNFZ, slip on all traces of this wide fault zone must be considered.

  9. Laser transformation hardening effect on hardening zone features and surface hardness of tool steel AISI D2

    Directory of Open Access Journals (Sweden)

    D. Lesyk

    2017-06-01

    Full Text Available The relationship of technological input regimes of the laser transformation hardening on change the hardening depth, hardening width, and hardening angle, as well as surface hardness of the tool steel AISI D2 using multifactor experiment with elements of the analysis of variance and regression equations was determined. The laser transformation hardening process implemented by controlling the heating temperature using Nd:YAG fiber laser with scanner, pyrometer and proportional-integral-differential controller. The linear and quadratic regression models are developed, as well as response surface to determine the effect of the heating temperature and feed rate of the treated surface on the energy density of the laser beam, hardening depths, hardening width, hardening angle, and surface hardness are designed. The main effect on the energy density of the laser beam has a velocity laser treatment, on the other hand, the main effect on the geometrical parameters of the laser hardened zone and surface hardness has temperature heating are shown. The optimum magnitudes of the heating temperature (1270 °C and feed rate of the treated surface (90 mm/min for laser transformation hardening of the tool steel AISI D2 using fiber laser with scanner were defined.

  10. Silver mirror reaction as an approach to construct a durable, robust superhydrophobic surface of bamboo timber with high conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Chunde; Li, Jingpeng [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Key Laboratory of Wood Science and Technology, Zhejiang Province (China); Han, Shenjie; Wang, Jin; Yao, Qiufang [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Sun, Qingfeng, E-mail: zafuqfsun@163.com [School of Engineering, Zhejiang Agricultural and Forestry University, Lin’an 311300 (China); Key Laboratory of Wood Science and Technology, Zhejiang Province (China)

    2015-06-25

    Highlights: • Ag NPs were deposited onto the surface of bamboo timber by silver mirror reaction. • The Ag NPs made the intrinsic insulating bamboo timber have a high conductivity. • The modified surfaces displayed superhydrophobicity even for corrosive solutions. - Abstract: Silver nanoparticles (Ag NPs) were successfully in situ deposited onto the surface of the bamboo timber through a simple silver mirror reaction. Scanning electron microscopy (SEM) images showed that the surface of the bamboo timber was densely covered with the uniform Ag NPs, which made the intrinsic insulating bamboo timber conductive. With further modification by fluoroalkylsilane (FAS), the Ag NPs-covered bamboo timber showed superhydrophobicity with the water contact angle (WCA) of 155°. Simultaneously, the modified bamboo timber displayed a durable and robust superhydrophobic property even under corrosive solutions including acidic, alkali and NaCl solutions with different molar concentrations. Especially in harsh conditions of boiling water or intense water stirring, the modified bamboo timber remained superhydrophobicity and high conductivity.

  11. Dimensionless model to determine spontaneous combustion danger zone in the longwall gob

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xin-hai; DENG Jun; WEN Hu

    2011-01-01

    According to spontaneous combustion propensity,the longwall gob is divided into three zones,including heat dissipation zone,self-heating zone and the choking zone.Only in the self-heating zone can temperature of coal rise due to oxidation.Studying the distribution of the “Three Zones” in gob is important for predicting and preventing spontaneous combustion in coalmine.In normal mining operations,temperature of coal is roughly constant.The process of mass transfer in the gob is considered to be steady.Based on mass conservation,gas species conservation,darcy' s law,Ficks law of diffusion and coal oxidation 1-grade reaction rule,governing equation for air leakage intensity and species concentration are deduced.With critical value of coal spontaneous combustion and the size of longwall workface as basic dimension,a dimensionless steady coupled model of air flow diffusion and chemical reaction in loose coal of Fully Mechanized Top-Coal Caving Mining Workface (FMTCCMW) is setup.By solving the model numerically,regulation of three zones' distribution and spontaneous combustion in the gob can be obtained.The results can be easily popularized to prediction of spontaneous combustion in other coalmines' longwall gob.

  12. Joint inversion of ambient noise surface wave and gravity data to image the upper crustal structure of the Tanlu fault zone to the southeast of Hefei, China

    Science.gov (United States)

    Wang, K.; Gu, N.; Zhang, H.; Zhou, G.

    2017-12-01

    The Tanlu fault is a major fault located in the eastern China, which stretches 2400 km long from Tancheng in the north to Lujiang in the south. It is generally believed that the Tanlu fault zone was formed in Proterozoic era and underwent a series of complicated processes since then. To understand the upper crustal structure around the southern segment of the Tanlu fault zone, in 2017 we deployed 53 short period seismic stations around the fault zone to the southeast of Hefei, capital city of Anhui province. The temporary array continuously recorded the data for about one month from 17 March to 26 April 2017. The seismic array spans an area of about 30km x 30Km with an average station spacing of about 5-6km. The vertical component data were used for extracting Rayleigh wave phase and group velocity dispersion data for the period of 0.2 to 5 seconds. To improve imaging the upper crustal structure of the fault zone, we jointly inverted the surface wave dispersion data and the gravity data because they have complementary strengths. To combine surface wave dispersion data and gravity observations into a single inversion framework, we used an empirical relationship between seismic velocity and density of Maceira and Ammon (2009). By finding the optimal relative weighting between two data types, we are able to find a shear wave velocity (Vs) model that fits both data types. The joint inversion can resolve the upper crustal fault zone structure down to about 7 km in depth. The Vs model shows that in this region the Tanlu fault is associated with high velocity anomalies, corresponding well to the Feidong complex seen on the surface. This indicates that the Tanlu fault zone may provide a channel for the intrusion of hot materials.

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

    Science.gov (United States)

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

    2013-06-07

    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 dehydrogenase were about 600 zmol and 30 amol, 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.

  14. Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

    Science.gov (United States)

    Favaro, Marco; Abdi, Fatwa F; Lamers, Marlene; Crumlin, Ethan J; Liu, Zhi; van de Krol, Roel; Starr, David E

    2018-01-18

    Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO 4 ) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO 4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO 4 /KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO 4 /KPi electrolyte interface.

  15. Quantitative surface analysis using deuteron-induced nuclear reactions

    International Nuclear Information System (INIS)

    Afarideh, Hossein

    1991-01-01

    The nuclear reaction analysis (NRA) technique consists of looking at the energies of the reaction products which uniquely define the particular elements present in the sample and it analysis the yield/energy distribution to reveal depth profiles. A summary of the basic features of the nuclear reaction analysis technique is given, in particular emphasis is placed on quantitative light element determination using (d,p) and (d,alpha) reactions. The experimental apparatus is also described. Finally a set of (d,p) spectra for the elements Z=3 to Z=17 using 2 MeV incident deutrons is included together with example of more applications of the (d,alpha) spectra. (author)

  16. Application of atomic mutations included in nuclear reactions, 40Ar(γ, p)39Cl(β decay)39Ar, to surface study

    International Nuclear Information System (INIS)

    Ohkuma, Juzo

    1987-01-01

    It has been found that the nuclear transformation processes which are initiated by photonuclear reactions can be used for studying the adsorption and chemical reactions taking place on solid surfaces. Chemically reactive 39 Cl was produced by irradiating 40 Ar with high-energy bremsstrahlung, and its blow was directed onto several material surfaces. The amount of chlorine adsorption was ascertained by detecting its radioactivity. Desorption without heating the adsorber samples inevitably occurred owing to the nuclear decay of 39 Cl. The adsorption and desorption rates were compared for several elements. A fast growth of oxide islands on sample surfaces was observed during the adsorption-desorption process. (author)

  17. Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

    Science.gov (United States)

    Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

    2010-03-10

    Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

  18. The application of white radiation to residual stress analysis in the intermediate zone between surface and volume

    CERN Document Server

    Genzel, C; Wallis, B; Reimers, W

    2001-01-01

    Mechanical surface processing is known to give rise to complex residual stress fields in the near surface region of polycrystalline materials. Consequently, their analysis by means of non-destructive X-ray and neutron diffraction methods has become an important topic in materials science. However, there remains a gap with respect to the accessible near surface zone, which concerns a range between about 10 mu m and 1 mm, where the conventional X-ray methods are no longer and the neutron methods are not yet sensitive. In order to achieve the necessary penetration depth tau to perform residual stress analysis (RSA) in this region, advantageous use can be made of energy dispersive X-ray diffraction of synchrotron radiation (15-60 keV) in the reflection mode. Besides an example concerning the adaptation of methods applied so far in the angle dispersive RSA to the energy dispersive case, the concept of a new materials science beamline at BESSY II for residual stress and texture analysis is presented.

  19. The application of white radiation to residual stress analysis in the intermediate zone between surface and volume

    International Nuclear Information System (INIS)

    Genzel, Ch.; Stock, C.; Wallis, B.; Reimers, W.

    2001-01-01

    Mechanical surface processing is known to give rise to complex residual stress fields in the near surface region of polycrystalline materials. Consequently, their analysis by means of non-destructive X-ray and neutron diffraction methods has become an important topic in materials science. However, there remains a gap with respect to the accessible near surface zone, which concerns a range between about 10 μm and 1 mm, where the conventional X-ray methods are no longer and the neutron methods are not yet sensitive. In order to achieve the necessary penetration depth τ to perform residual stress analysis (RSA) in this region, advantageous use can be made of energy dispersive X-ray diffraction of synchrotron radiation (15-60 keV) in the reflection mode. Besides an example concerning the adaptation of methods applied so far in the angle dispersive RSA to the energy dispersive case, the concept of a new materials science beamline at BESSY II for residual stress and texture analysis is presented

  20. The role of fluctuations in bistability and oscillations during the H{sub 2} + O{sub 2} reaction on nanosized rhodium crystals

    Energy Technology Data Exchange (ETDEWEB)

    Grosfils, P.; Gaspard, P. [Center for Nonlinear Phenomena and Complex Systems (CENOLI), Université libre de Bruxelles (ULB), Campus Plaine Code Postal 231, B-1050 Brussels (Belgium); Visart de Bocarmé, T. [Center for Nonlinear Phenomena and Complex Systems (CENOLI) and Chemical Physics of Materials—Catalysis and Tribology, Université libre de Bruxelles (ULB), Campus Plaine Code Postal 243, B-1050 Brussels (Belgium)

    2015-08-14

    A combined experimental and theoretical study is presented of fluctuations observed by field ion microscopy in the catalytic reaction of water production on a rhodium tip. A stochastic approach is developed to provide a comprehensive understanding of the different phenomena observed in the experiment, including burst noise manifesting itself in a bistability regime, noisy oscillations, and nanopatterns with a cross-like oxidized zone separating the surface into four quadrants centered on the (111) facets. The study is based on a stochastic model numerically simulating the processes of adsorption, desorption, reaction, and transport. The surface diffusion of hydrogen is described as a percolation process dominated by large clusters corresponding to the four quadrants. The model reproduces the observed phenomena in the ranges of temperature, pressures, and electric field of the experiment.

  1. Reductive dechlorination of trichloroethene DNAPL source zones: source zone architecture versus electron donor availability

    Science.gov (United States)

    Krol, M.; Kokkinaki, A.; Sleep, B.

    2014-12-01

    The persistence of dense-non-aqueous-phase liquids (DNAPLs) in the subsurface has led practitioners and regulatory agencies to turn towards low-maintenance, low-cost remediation methods. Biological degradation has been suggested as a possible solution, based on the well-proven ability of certain microbial species to break down dissolved chlorinated ethenes under favorable conditions. However, the biodegradation of pure phase chlorinated ethenes is subject to additional constraints: the continuous release of electron acceptor at a rate governed by mass transfer kinetics, and the temporal and spatial heterogeneity of DNAPL source zones which leads to spatially and temporally variable availability of the reactants for reductive dechlorination. In this work, we investigate the relationship between various DNAPL source zone characteristics and reaction kinetics using COMPSIM, a multiphase groundwater model that considers non-equilibrium mass transfer and Monod-type kinetics for reductive dechlorination. Numerical simulations are performed for simple, homogeneous trichloroethene DNAPL source zones to demonstrate the effect of single source zone characteristics, as well as for larger, more realistic heterogeneous source zones. It is shown that source zone size, and mass transfer kinetics may have a decisive effect on the predicted bio-enhancement. Finally, we evaluate the performance of DNAPL bioremediation for realistic, thermodynamically constrained, concentrations of electron donor. Our results indicate that the latter may be the most important limitation for the success of DNAPL bioremediation, leading to reduced bio-enhancement and, in many cases, comparable performance with water flooding.

  2. T Tank Farm Interim Surface Barrier Demonstration -- Vadose Zone Monitoring FY07 Report

    International Nuclear Information System (INIS)

    Zhang, Z. F.; Strickland, Christopher E.; Keller, Jason M.; Wittreich, Curtis D.; Sydnor, Harold A.

    2008-01-01

    CH2M HILL Hanford Group, Inc. is currently in the process of constructing a temporary surface barrier over a portion of the T Tank Farm as part of the T farm Interim Surface Barrier Demonstration Project. The surface barrier is designed to prevent the infiltration of precipitation into the contaminated soil zone created by the Tank T-106 leak and minimize movement of the contamination. As part of the demonstration effort, vadose zone moisture monitoring is being performed to assess the effectiveness of the barrier at reducing soil moisture. A solar-powered and remotely-controlled system was installed to continuously monitor soil water conditions in four instrument nests (i.e., A, B, C, and D) and the site meteorological condition. Each instrument nest was composed of a capacitance probe with multiple sensors, multiple heat-dissipation units, a neutron probe access tube and a datalogger. Nests A and B also contained a drain gauge each. The principle variables monitored for this purpose are soil-water content, soil-water pressure, and soil-water flux. In addition to these, soil temperature, precipitation, and air temperature are measured. Data from each of the dataloggers were transmitted remotely to the receiving computer. The neutron probe access tube was used to perform quarterly manual measurements of soil-water content using a neutron probe. This monitoring system was used to assess the soil water conditions in the soil outside and within the footprint of the surface barrier to be emplaced in the Hanford T Tank Farm. Data to date is baseline under the condition without the interim surface barrier in place. All the instruments except the two drain gauges were functional in FY07. The capacitance-probe measurements showed that the soil-moisture content at relatively shallow depths (e.g., 0.6 and 0.9 m) was increasing since October 2006 and reached the highest in early January 2007 followed by a slight decrease. Soil-moisture contents at the depths of 1.3 m and

  3. Surface runoff water quality in a managed three zone riparian buffer.

    Science.gov (United States)

    Lowrance, Richard; Sheridan, Joseph M

    2005-01-01

    Managed riparian forest buffers are an important conservation practice but there are little data on the water quality effects of buffer management. We measured surface runoff volumes and nutrient concentrations and loads in a riparian buffer system consisting of (moving down slope from the field) a grass strip, a managed forest, and an unmanaged forest. The managed forest consisted of sections of clear-cut, thinned, and mature forest. The mature forest had significantly lower flow-weighted concentrations of nitrate, ammonium, total Kjeldahl N (TKN), sediment TKN, total N (nitrate + TKN), dissolved molybdate reactive P (DMRP), total P, and chloride. The average buffer represented the conditions along a stream reach with a buffer system in different stages of growth. Compared with the field output, flow-weighted concentrations of nitrate, ammonium, DMRP, and total P decreased significantly within the buffer and flow-weighted concentrations of TKN, total N, and chloride increased significantly within the buffer. All loads decreased significantly from the field to the middle of the buffer, but most loads increased from the middle of the buffer to the sampling point nearest the stream because surface runoff volume increased near the stream. The largest percentage reduction of the incoming nutrient load (at least 65% for all nutrient forms) took place in the grass buffer zone because of the large decrease (68%) in flow. The average buffer reduced loadings for all nutrient species, from 27% for TKN to 63% for sediment P. The managed forest and grass buffer combined was an effective buffer system.

  4. DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

    Science.gov (United States)

    Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

    2017-09-24

    We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

  5. The speciation of Si and other alloying elements in the oxide surface film of galvanically corroded weld fusion zone of laser welded AA6061 aluminium alloy

    Energy Technology Data Exchange (ETDEWEB)

    Mujibur Rahman, A.B.M.; Kumar, Sunil [Ian Wark Research Institute, University of South Australia, Mawson Lakes Campus, Mawson Lakes, South Australia 5095 (Australia); Gerson, Andrea R. [Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes Campus, Mawson Lakes, South Australia 5095 (Australia)], E-mail: Andrea.Gerson@unisa.edu.au

    2008-05-15

    It has recently been proposed that on galvanic corrosion of laser weldments of AA6061 aluminium alloy the temporal increase in galvanic corrosion resulted from either the build up of intermetallic phases in the surface oxide layer and/or a significant increase in the surface area of the cathodic weld fusion zone due to the porous nature of the surface layer. This proposition has motivated a comprehensive surface analytical study of the incorporation of alloying elements into the oxide surface film, which is composed predominately of alumina. Si is found to be present as silicate and silicides. The Gibbs free energy of formation, per cation, of silicate is more negative than that for alumina and hence silicate formation is thermodynamically, relatively, favourable. In contrast the Gibbs free energy for oxide formation, per cation, for the other alloying elements is less negative and hence relatively unfavourable compared to the formation of alumina. We propose therefore that Fe, Cu and Cr are present in the metallic form, possibly as silicides, within the oxide surface layer. Magnesium is found to be depleted relative to the weld fusion zone presumably due to dissolution within the electrolyte.

  6. The speciation of Si and other alloying elements in the oxide surface film of galvanically corroded weld fusion zone of laser welded AA6061 aluminium alloy

    International Nuclear Information System (INIS)

    Mujibur Rahman, A.B.M.; Kumar, Sunil; Gerson, Andrea R.

    2008-01-01

    It has recently been proposed that on galvanic corrosion of laser weldments of AA6061 aluminium alloy the temporal increase in galvanic corrosion resulted from either the build up of intermetallic phases in the surface oxide layer and/or a significant increase in the surface area of the cathodic weld fusion zone due to the porous nature of the surface layer. This proposition has motivated a comprehensive surface analytical study of the incorporation of alloying elements into the oxide surface film, which is composed predominately of alumina. Si is found to be present as silicate and silicides. The Gibbs free energy of formation, per cation, of silicate is more negative than that for alumina and hence silicate formation is thermodynamically, relatively, favourable. In contrast the Gibbs free energy for oxide formation, per cation, for the other alloying elements is less negative and hence relatively unfavourable compared to the formation of alumina. We propose therefore that Fe, Cu and Cr are present in the metallic form, possibly as silicides, within the oxide surface layer. Magnesium is found to be depleted relative to the weld fusion zone presumably due to dissolution within the electrolyte

  7. Modifying surface resistivity and liquid moisture management property of keratin fibers through thiol-ene click reactions.

    Science.gov (United States)

    Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

    2014-01-22

    This paper reports on a new method for improving the antistatic and liquid moisture management properties of keratinous materials. The method involves the generation of thiols by controlled reduction of cystine disulfide bonds in keratin with tris(2-carboxyethyl) phosphine hydrochloride and subsequent grafting of hydrophilic groups onto the reduced keratin by reaction with an acrylate sulfonate or acrylamide sulfonate through thiol-ene click chemistry. The modified substrates were characterized with Raman spectroscopy and scanning electron microscopy and evaluated for their performance changes in liquid moisture management, surface resistivity, and wet burst strength. The results have revealed that the thiol-acrylate reaction is more efficient than the thiol-acrylamide reaction, and the keratinous substrate modified with an acrylate sulfonate salt exhibits significantly improved antistatic and liquid moisture management properties.

  8. Simultaneous hydrogen and methanol enhancement through a recuperative two-zone thermally coupled membrane reactor

    Energy Technology Data Exchange (ETDEWEB)

    Bayat, M. [Shiraz University, Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz (Iran, Islamic Republic of); Rahimpour, M.R. [Shiraz University, Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz (Iran, Islamic Republic of); Shiraz University, Gas Center of Excellence, Shiraz (Iran, Islamic Republic of)

    2012-12-15

    In this work, a novel configuration with two zones instead of one single integrated catalytic bed in thermally coupled membrane reactor (TCMR) is developed for enhancement of simultaneous methanol, benzene and hydrogen production. In the first zone, the synthesis gas is partly converted to methanol in a conventional water-cooled reactor. In the second zone, the reaction heat is used to drive the endothermic dehydrogenation of cyclohexane reaction in second tube side. Selective permeation of hydrogen through the Pd-Ag membrane is achieved by co-current flow of sweep gas through the permeation side. The length of first zone is chosen equal 35 cm which the optimization procedure obtained this value. The proposed model has been used to compare the performance of a two-zone thermally coupled membrane reactor (TZTCMR) with conventional reactor (CR) and TCMR at identical process conditions. The simulation results represent 13.14 % enhancement in the production of pure hydrogen in comparison with TCMR. Moreover, 2.96 and 4.54 % enhancement of the methanol productivity relative to TCMR and CR were seen, respectively, owing to utilizing higher temperature at the first parts of reactor for higher reaction rate and then reducing temperature gradually at the end parts of reactor for increasing thermodynamics equilibrium conversion in TZTCMR. (orig.)

  9. Mechanical properties of fracture zones

    International Nuclear Information System (INIS)

    Leijon, B.

    1993-05-01

    Available data on mechanical characteristics of fracture zones are compiled and discussed. The aim is to improve the basis for adequate representation of fracture zones in geomechanical models. The sources of data researched are primarily borehole investigations and case studies in rock engineering, involving observations of fracture zones subjected to artificial load change. Boreholes only yield local information about the components of fracture zones, i.e. intact rock, fractures and various low-strength materials. Difficulties are therefore encountered in evaluating morphological and mechanical properties of fracture zones from borehole data. Although often thought of as macroscopically planar features, available field data consistently show that fracture zones are characterized by geometrical irregularities such as thickness variations, surface undulation and jogs. These irregularities prevail on all scales. As a result, fracture zones are on all scales characterized by large, in-plane variation of strength- and deformational properties. This has important mechanical consequences in terms of non-uniform stress transfer and complex mechanisms of shear deformation. Field evidence for these findings, in particular results from the underground research laboratory in Canada and from studies of induced fault slip in deep mines, is summarized and discussed. 79 refs

  10. Characterizing the structural maturity of fault zones using high-resolution earthquake locations.

    Science.gov (United States)

    Perrin, C.; Waldhauser, F.; Scholz, C. H.

    2017-12-01

    We use high-resolution earthquake locations to characterize the three-dimensional structure of active faults in California and how it evolves with fault structural maturity. We investigate the distribution of aftershocks of several recent large earthquakes that occurred on immature faults (i.e., slow moving and small cumulative displacement), such as the 1992 (Mw7.3) Landers and 1999 (Mw7.1) Hector Mine events, and earthquakes that occurred on mature faults, such as the 1984 (Mw6.2) Morgan Hill and 2004 (Mw6.0) Parkfield events. Unlike previous studies which typically estimated the width of fault zones from the distribution of earthquakes perpendicular to the surface fault trace, we resolve fault zone widths with respect to the 3D fault surface estimated from principal component analysis of local seismicity. We find that the zone of brittle deformation around the fault core is narrower along mature faults compared to immature faults. We observe a rapid fall off of the number of events at a distance range of 70 - 100 m from the main fault surface of mature faults (140-200 m fault zone width), and 200-300 m from the fault surface of immature faults (400-600 m fault zone width). These observations are in good agreement with fault zone widths estimated from guided waves trapped in low velocity damage zones. The total width of the active zone of deformation surrounding the main fault plane reach 1.2 km and 2-4 km for mature and immature faults, respectively. The wider zone of deformation presumably reflects the increased heterogeneity in the stress field along complex and discontinuous faults strands that make up immature faults. In contrast, narrower deformation zones tend to align with well-defined fault planes of mature faults where most of the deformation is concentrated. Our results are in line with previous studies suggesting that surface fault traces become smoother, and thus fault zones simpler, as cumulative fault slip increases.

  11. Structural Mapping Along the Central San Andreas Fault-zone Using Airborne Electromagnetics

    Science.gov (United States)

    Zamudio, K. D.; Bedrosian, P.; Ball, L. B.

    2017-12-01

    Investigations of active fault zones typically focus on either surface expressions or the associated seismogenic zones. However, the largely aseismic upper kilometer can hold significant insight into fault-zone architecture, strain partitioning, and fault-zone permeability. Geophysical imaging of the first kilometer provides a link between surface fault mapping and seismically-defined fault zones and is particularly important in geologically complex regions with limited surface exposure. Additionally, near surface imaging can provide insight into the impact of faulting on the hydrogeology of the critical zone. Airborne electromagnetic (AEM) methods offer a unique opportunity to collect a spatially-large, detailed dataset in a matter of days, and are used to constrain subsurface resistivity to depths of 500 meters or more. We present initial results from an AEM survey flown over a 60 kilometer long segment of the central San Andreas Fault (SAF). The survey is centered near Parkfield, California, the site of the SAFOD drillhole, which marks the transition between a creeping fault segment to the north and a locked zone to the south. Cross sections with a depth of investigation up to approximately 500 meters highlight the complex Tertiary and Mesozoic geology that is dismembered by the SAF system. Numerous fault-parallel structures are imaged across a more than 10 kilometer wide zone centered on the surface trace. Many of these features can be related to faults and folds within Plio-Miocene sedimentary rocks found on both sides of the fault. Northeast of the fault, rocks of the Mesozoic Franciscan and Great Valley complexes are extremely heterogeneous, with highly resistive volcanic rocks within a more conductive background. The upper 300 meters of a prominent fault-zone conductor, previously imaged to 1-3 kilometers depth by magnetotellurics, is restricted to a 20 kilometer long segment of the fault, but is up to 4 kilometers wide in places. Elevated fault-zone

  12. The relationship between Anopheles gambiae density and rice cultivation in the savannah zone and forest zone of Côte d'Ivoire.

    Science.gov (United States)

    Briët, Olivier J T; Dossou-Yovo, Joel; Akodo, Elena; van de Giesen, Nick; Teuscher, Thomas M

    2003-05-01

    In 13 villages in the savannah zone and 21 villages in the forest zone of Côte d'Ivoire, the biting density of the principal malaria vector, Anopheles gambiae, was studied as a function of rice cultivation in the inland valleys in a 2-km radius around each village. In the savannah villages, during the main season cropping period, surface water on rice-cultivated and to a lesser extent on uncultivated inland valleys seems to contribute strongly to the A. gambiae population density. For the off-season cropping period (which starts after the first light rains in the savannah zone), correlations were weaker. Breeding sites other than in inland valleys may play an important role in the savannah zone. In the forest zone, however, the A. gambiae population density was strongly correlated with the surface water availability (SWA) in the rice-cultivated inland valleys, whereas the correlation with the SWA in other (uncultivated) inland valleys was weak. The requirement of sunlit breeding sites for A. gambiae might explain this difference between zones. In the forest zone, only inland valleys cleared for rice cultivation meet this requirement, whereas all other inland valleys are covered with dense vegetation. In the savannah zone, however, most undergrowth is burnt during the dry season, which permits sunlight to reach puddles resulting from the first rains.

  13. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  14. Three key points along an intrinsic reaction coordinate

    Indian Academy of Sciences (India)

    Unknown

    Abstract. The concept of the reaction force is presented and discussed in detail. For typical processes with energy barriers, it has a universal form which defines three key points along an intrinsic reaction co- ordinate: the force minimum, zero and maximum. We suggest that the resulting four zones be interpreted as involving ...

  15. Application of InSAR and Gravimetry for Land Subsidence Hazard Zoning in Aguascalientes, Mexico

    Directory of Open Access Journals (Sweden)

    Jesús Pacheco-Martínez

    2015-12-01

    Full Text Available In this work we present an application of InSAR and gravimetric surveys for risk management related to land subsidence and surface ground faulting generation. A subsidence velocity map derived from the 2007–2011 ALOS SAR imagery and a sediment thicknesses map obtained from the inversion of gravimetric data were integrated with a surface fault map to produce a subsidence hazard zoning in the city of Aguascalientes, Mexico. The resulting zoning is presented together with specific recommendations about geotechnical studies needed for further evaluation of surface faulting in these hazard zones. The derived zoning map consists in four zones including null hazard (stable terrain without subsidence, low hazard (areas prone to subsidence, medium hazard (zones with subsidence and high hazard (zones with surface faulting. InSAR results displayed subsidence LOS velocities up to 10 cm/year and two subsidence areas unknown before this study. Gravimetric results revealed that the thicker sediment sequence is located toward north of Aguascalientes City reaching up to 600 m in thickness, which correspond to a high subsidence LOS velocity zone (up to 6 cm/year.

  16. Neural network approach to time-dependent dividing surfaces in classical reaction dynamics

    Science.gov (United States)

    Schraft, Philippe; Junginger, Andrej; Feldmaier, Matthias; Bardakcioglu, Robin; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

    2018-04-01

    In a dynamical system, the transition between reactants and products is typically mediated by an energy barrier whose properties determine the corresponding pathways and rates. The latter is the flux through a dividing surface (DS) between the two corresponding regions, and it is exact only if it is free of recrossings. For time-independent barriers, the DS can be attached to the top of the corresponding saddle point of the potential energy surface, and in time-dependent systems, the DS is a moving object. The precise determination of these direct reaction rates, e.g., using transition state theory, requires the actual construction of a DS for a given saddle geometry, which is in general a demanding methodical and computational task, especially in high-dimensional systems. In this paper, we demonstrate how such time-dependent, global, and recrossing-free DSs can be constructed using neural networks. In our approach, the neural network uses the bath coordinates and time as input, and it is trained in a way that its output provides the position of the DS along the reaction coordinate. An advantage of this procedure is that, once the neural network is trained, the complete information about the dynamical phase space separation is stored in the network's parameters, and a precise distinction between reactants and products can be made for all possible system configurations, all times, and with little computational effort. We demonstrate this general method for two- and three-dimensional systems and explain its straightforward extension to even more degrees of freedom.

  17. Radioactive waste isolation in arid zones

    International Nuclear Information System (INIS)

    Nativ, R.

    1991-01-01

    Arid zones are currently considered ideal sites for the isolation of radioactive and other hazardous wastes. Because arid zones have low precipitation, other hydrological features such as minimal surface water, low recharge rates, small hydraulic gradients, deep water table and lower water quality are also inferred. These premises have proved to be misleading in many circumstances, resulting in groundwater contamination by radionuclides. Case studies indicating surface water damages, occurrence of active recharge, groundwater flow and considerable discharge of potable water in arid and hyper-arid terrains, as well as the possibility of future climatic changes, require careful hydrological assessment of proposed sites in arid areas. (author)

  18. Understanding the mechanisms of solid-water reactions through analysis of surface topography.

    Science.gov (United States)

    Bandstra, Joel Z; Brantley, Susan L

    2015-12-01

    The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic

  19. [Ciliate diversity and spatiotemporal variation in surface sediments of Yangtze River estuary hypoxic zone].

    Science.gov (United States)

    Feng, Zhao; Kui-Dong, Xu; Zhao-Cui, Meng

    2012-12-01

    By using denaturing gradient gel electrophoresis (DGGE) and sequencing as well as Ludox-QPS method, an investigation was made on the ciliate diversity and its spatiotemporal variation in the surface sediments at three sites of Yangtze River estuary hypoxic zone in April and August 2011. The ANOSIM analysis indicated that the ciliate diversity had significant difference among the sites (R = 0.896, P = 0.0001), but less difference among seasons (R = 0.043, P = 0.207). The sequencing of 18S rDNA DGGE bands revealed that the most predominant groups were planktonic Choreotrichia and Oligotrichia. The detection by Ludox-QPS method showed that the species number and abundance of active ciliates were maintained at a higher level, and increased by 2-5 times in summer, as compared with those in spring. Both the Ludox-QPS method and the DGGE technique detected that the ciliate diversity at the three sites had the similar variation trend, and the Ludox-QPS method detected that there was a significant variation in the ciliate species number and abundance between different seasons. The species number detected by Ludox-QPS method was higher than that detected by DGGE bands. Our study indicated that the ciliates in Yangtze River estuary hypoxic zone had higher diversity and abundance, with the potential to supply food for the polyps of jellyfish.

  20. The habitable zone and extreme planetary orbits.

    Science.gov (United States)

    Kane, Stephen R; Gelino, Dawn M

    2012-10-01

    The habitable zone for a given star describes the range of circumstellar distances from the star within which a planet could have liquid water on its surface, which depends upon the stellar properties. Here we describe the development of the habitable zone concept, its application to our own solar system, and its subsequent application to exoplanetary systems. We further apply this to planets in extreme eccentric orbits and show how they may still retain life-bearing properties depending upon the percentage of the total orbit which is spent within the habitable zone. Key Words: Extrasolar planets-Habitable zone-Astrobiology.

  1. Air-sea interactions in the marginal ice zone

    Directory of Open Access Journals (Sweden)

    Seth Zippel

    2016-03-01

    Full Text Available Abstract The importance of waves in the Arctic Ocean has increased with the significant retreat of the seasonal sea-ice extent. Here, we use wind, wave, turbulence, and ice measurements to evaluate the response of the ocean surface to a given wind stress within the marginal ice zone, with a focus on the local wind input to waves and subsequent ocean surface turbulence. Observations are from the Beaufort Sea in the summer and early fall of 2014, with fractional ice cover of up to 50%. Observations showed strong damping and scattering of short waves, which, in turn, decreased the wind energy input to waves. Near-surface turbulent dissipation rates were also greatly reduced in partial ice cover. The reductions in waves and turbulence were balanced, suggesting that a wind-wave equilibrium is maintained in the marginal ice zone, though at levels much less than in open water. These results suggest that air-sea interactions are suppressed in the marginal ice zone relative to open ocean conditions at a given wind forcing, and this suppression may act as a feedback mechanism in expanding a persistent marginal ice zone throughout the Arctic.

  2. Human reactions to electromagnetic radiation in millimeter range

    Energy Technology Data Exchange (ETDEWEB)

    Andreev, E.A.; Belyy, M.U.; Sit' ko, S.P.

    1985-01-01

    The article deals with a problem that is on the boundary of different disciplines. The authors discovered previously unknown effects of low-energy electromagnetic radiation on the human body. A total of 188 subjects, both healthy and sick in terms of medical diagnosis, were submitted to sensory tests. The vast majority of healthy subjects did not react to radiation in the range of 27-78 GHz and power density of up to 10 mW/cm/sup 2/. The same situation was also observed in many cases with patients. However, exposure of very specific parts of the body of sick subjects to electromagnetic waves at a fixed frequency in the range of 45-65 GHz elicited a sensory reaction in the region of the organ with a marked impairment, and this was an organ that was spatially remote from the irradiated region. It was established that the zones on the surface of the body that are the most sensitive to radiation coincide with acupuncture zones that are known in reflex acupuncture therapy. In addition to presentation of experimental results, the authors also propose a theoretical interpretation of the demonstrated effects.

  3. Theoretical analysis of recirculation zone and buffer zone in the ADS windowless spallation target

    International Nuclear Information System (INIS)

    Liu, Jie; Pan, Chang-zhao; Tong, Jian-fei; Lu, Wen-qiang

    2015-01-01

    Highlights: • Height of recirculation zone is very important in windowless target design. • A theoretical formula for the height is derived based on the Bernoulli equation. • Numerical simulation for the LBE is performed and the height of recirculation zone is also obtained. • The theoretically-derived simulation-predicted recirculation zone heights agree with each other very well and the theoretical derivation is proved to be correct. - Abstract: The thermo-hydraulic analysis including reduction of the height of recirculation zone and stability of the free surface is very important in the design and optimization of ADS windowless spallation targets. In the present study, the Bernoulli equation is used to analyze the entire flow process in the target. Formulae for the height of the recirculation zone and the buffer zone are both obtained explicitly. Furthermore, numerical simulation for the heavy metal lead–bismuth eutectic liquid and vapor with cavitation phase change is also performed, and a novel method to calculate the height of the recirculation zone is put forward. By comparison of the theoretical formulae and numerical results, it is clearly shown that they agree with each other very well, and the heights predicted by the two methods are both determined by their own upstream flow parameters

  4. Surface displacements and energy release rates for constant stress drop slip zones in joined elastic quarter spaces

    Science.gov (United States)

    Rodgers, Michael J.; Wen, Shengmin; Keer, Leon M.

    2000-08-01

    A three-dimensional quasi-static model of faulting in an elastic half-space with a horizontal change of material properties (i.e., joined elastic quarter spaces) is considered. A boundary element method is used with a stress drop slip zone approach so that the fault surface relative displacements as well as the free surface displacements are approximated in elements over their respective domains. Stress intensity factors and free surface displacements are calculated for a variety of cases to show the phenomenological behavior of faulting in such a medium. These calculations showed that the behavior could be distinguished from a uniform half-space. Slip in a stiffer material increases, while slip in a softer material decreases the energy release rate and the free surface displacements. Also, the 1989 Kalapana earthquake was located on the basis of a series of forward searches using this method and leveling data. The located depth is 8 km, which is the closer to the seismically inferred depth than that determined from other models. Finally, the energy release rate, which can be used as a fracture criterion for fracture at this depth, is calculated to be 11.1×106 J m-2.

  5. Effects of polishing on surface roughness, gloss and color of surface reaction type pre-reacted glass-ionomer filled resin composite.

    Science.gov (United States)

    Hosoya, Yumiko; Shiraishi, Takanobu; Odatsu, Tetsuro; Miyazaki, Masashi; García-Godoy, Franklin

    2011-06-01

    To evaluate the effects of polishing on surface roughness, gloss and color of different shades of surface reaction type pre-reacted glass-ionomer (S-PRG) filled nano-hybrid resin composite. Resin disks of 15 mm diameter and 2 mm thickness and final polish with 1000-grit SiC paper, super fine cut diamond (FG) point, silicon (MFR) point and Super-Snap mini-disk red (SNAP) were made with Beautifil II shades: A2, A20, Inc). One week after curing, the surface roughness, gloss and color were measured. Data was analyzed with ANOVA and Fisher's PLSD with alpha= 0.05 For all shades, the order of roughness (Ra) ranked according to groups of 1000-grit SiC > FG > MFR > SNAP with significant differences among all groups. For all shades, the order of gloss ranked according to groups of SNAP > MFR > FG > 1000-grit SiC with significant differences among the groups except for between MFR and FG without significant difference. The influence of the surface roughness on color differed among the polishing groups and shades. However, the values of the color differences (deltaE*ab) between the polishing groups of all shades were imperceptible to the naked eye.

  6. 33 CFR 165.1141 - Safety Zone; San Clemente 3 NM Safety Zone, San Clemente Island, CA.

    Science.gov (United States)

    2010-07-01

    ...) Location. The following area is a safety zone: All waters of the Pacific Ocean surrounding San Clemente Island, from surface to bottom, extending from the high tide line on the island seaward 3 NM. The zone... 3 NM from the high tide line to 33°02.82′ N, 118°30.65′ W; thence 33°01.29′ N, 118°33.88′ W; thence...

  7. Colour and surface fluorescence development and their relationship with Maillard reaction markers as influenced by structural changes during cornflakes production.

    Science.gov (United States)

    Farroni, Abel; Buera, María Del Pilar

    2012-12-01

    The aim of this work was to study colour and surface fluorescence development in relation to the chemical markers for the Maillard reaction at the cooking, flaking and toasting stages of cornflake production process. Colour was measured by a calibrated computer vision system. Surface fluorescence was measured on compressed samples. Aqueous extracted Maillard reaction markers (hydroxymethylfurfural, carboxymethyl-lysine, absorbance at 420nm and total fluorescence) were measured on protease hydrolyzed samples. Sample microstructure was observed by scanning electron microscopy. During cooking the colour coordinates L(∗) and b(∗) decreased and a(∗) increased. After flaking, the samples appeared lighter, while the pigment concentration, fluorescence and hydroxymethylfurfural did not change. Toasting generated bubbles in the matrix and L(∗) apparently increased, although brown pigment concentration increased. Pigment concentration did not correlate with surface colour due to the destruction or generation of interfaces. Surface and microstructure effects can be avoided by milling and compressing the samples. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Near Surface Geophysical Investigations of Potential Direct Recharge Zones in the Biscayne Aquifer within Everglades National Park, Florida.

    Science.gov (United States)

    Mount, G.; Comas, X.

    2017-12-01

    The karstic Miami Limestone of the Biscayne aquifer is characterized as having water flow that is controlled by the presence of dissolution enhanced porosity and mega-porous features. The dissolution features and other high porosity areas create horizontal preferential flow paths and high rates of ground water velocity, which may not be accurately conceptualized in groundwater flow models. In addition, recent research suggests the presence of numerous vertical dissolution features across Everglades National Park at Long Pine Key Trail, that may act as areas of direct recharge to the aquifer. These vertical features have been identified through ground penetrating radar (GPR) surveys as areas of velocity pull-down which have been modeled to have porosity values higher than the surrounding Miami Limestone. As climate change may induce larger and longer temporal variability between wet and dry times in the Everglades, a more comprehensive understanding of preferential flow pathways from the surface to the aquifer would be a great benefit to modelers and planners. This research utilizes near surface geophysical techniques, such as GPR, to identify these vertical dissolution features and then estimate the spatial variability of porosity using petrophysical models. GPR transects that were collected for several kilometers along the Long Pine Key Trail, show numerous pull down areas that correspond to dissolution enhanced porosity zones within the Miami Limestone. Additional 3D GPR surveys have attempted to delineate the boundaries of these features to elucidate their geometry for future modelling studies. We demonstrate the ability of near surface geophysics and petrophysical models to identify dissolution enhanced porosity in shallow karstic limestones to better understand areas that may act as zones of direct recharge into the Biscayne Aquifer.

  9. Construction, specification, and mathematical description of aspheric surfaces.

    Science.gov (United States)

    Smith, G; Atchison, D A

    1983-03-01

    Rotationally symmetrical aspheric surfaces of spectacle lenses are constructed as either "zonal aspherics" or "continuous aspherics." Zonal aspherics consist of annular zones surrounding a central zone with each zone being nominally spherical with progressively lower surface power the farther the zone is from the surface vertex. Aspheric surfaces are often specified by the radial drop in surface power from the center to the edge of the lens (e.g., Welsh Four-drop), but for assessment purposes the surface shape must be specified more precisely. The formulas for the description of continuous aspherics can be manipulated into different forms. Mathematical descriptions are given or developed which will enable theoretical assessment of the performances of all lenses with rotationally symmetrical aspheric surfaces.

  10. Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

    Science.gov (United States)

    Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

    2016-08-01

    A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Characterizing multiple sources and interaction in the critical zone through Sr-isotope tracing of surface and groundwater

    Science.gov (United States)

    Negrel, Philippe; Pauwels, Hélène

    2017-04-01

    The Critical Zone (CZ) is the lithosphere-atmosphere boundary where complex physical, chemical and biological processes occurs and control the transfer and storage of water and chemical elements. This is the place where life-sustaining resources are, where nutrients are being released from the rocks. Because it is the place where we are living, this is a fragile zone, a critical zone as a perturbed natural ecosystem. Water resources in hard-rocks commonly involve different hydrogeological compartments such as overlying sediments, weathered rock, the weathered-fissured zone, and fractured bedrock. Streams, lakes and wetlands that drain such environments can drain groundwater, recharge groundwater, or do both. Groundwater resources in many countries are increasingly threatened by growing demand, wasteful use, and contamination. Surface water and shallow groundwater are particularly vulnerable to pollution, while deeper resources are more protected from contamination. Here, we first report on Sr isotope data as well as major ions, from shallow and deep groundwater in several granite and schist areas over France with intensive agriculture covering large parts of these catchments. In three granite and Brioverian 'schist' areas of the Armorican Massif, the range in Sr contents in groundwater from different catchments agrees with previous work on groundwater sampled from granites in France. The Sr content is well correlated with Mg and both are partly related to agricultural practices and water rock interaction. The relationship between Sr- isotope and Mg/Sr ratios allow defining the different end-members, mainly rain, agricultural practice and water-rock interaction. The data from the Armorican Massif and other surface and groundwater for catchment draining silicate bedrocks (300-450Ma) like the Hérault, Seine, Moselle, Garonne, Morvan, Margeride, Cantal, Pyrénées and Vosges are scattered between at least three geochemical signatures. These include fertilizer and

  12. The effect of surface anisotropy in the slippery zone of Nepenthes alata pitchers on beetle attachment

    Directory of Open Access Journals (Sweden)

    Elena V. Gorb

    2011-06-01

    Full Text Available The slippery zone in pitchers of the carnivorous plant Nepenthes alata bears scattered prominent lunate cells and displays continuous epicuticular crystalline wax coverage. The aim of this study was to examine the influence of the surface anisotropy, caused by the shape of lunate cells, on insect attachment ability. Traction tests with ladybird beetles Coccinella septempunctata were performed in two types of experiments, where surface samples of (1 intact pitchers, (2 chemically de-waxed pitchers, and (3 their polymer replicas were placed horizontally. Beetle traction forces were measured when they walked on test surfaces in either an upward (towards the peristome or downward (towards the pitcher bottom direction, corresponding to the upright or inverted positions of the pitcher. On intact pitcher surfaces covered with both lunate cells and wax crystals, experiments showed significantly higher forces in the direction towards the pitcher bottom. To distinguish between the contributions, from claw interlocking and pad adhesion, to insect attachment on the pitcher surfaces, intact versus claw-ablated beetles were used in the second type of experiment. On both de-waxed plant samples and their replicas, intact insects generated much higher forces in the downward direction compared to the upward one, whereas clawless insects did not. These results led to the conclusion that, (i due to the particular shape of lunate cells, the pitcher surface has anisotropic properties in terms of insect attachment, and (ii claws were mainly responsible for attachment enhancement in the downward pitcher direction, since, in this direction, they could interlock with overhanging edges of lunate cells.

  13. The real value of nuclear-weapon-free zones

    International Nuclear Information System (INIS)

    Carasales, J.

    1998-01-01

    The international community has greeted the establishment of two new nuclear weapon-free zones with praise. Africa and South Asia are the regions which will join, once the respective treaties are ratified and in force, Latin America and the South Pacific to ensure that extensive areas of the earth remain free of nuclear weapons. The usual reaction to these accomplishments is to hail them as important contributions to international peace and security, and as meaningful steps towards a world free of nuclear weapons. The nuclear weapon-free zones have their value but this value relates mainly to the countries within the zone. The interest of nuclear-weapon states are not really affected, or, if they are, the influence is not significant. One should bear in mind that the really important and meaningful nuclear weapon-free zones have yet to be achieved

  14. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    Science.gov (United States)

    Harvey, Judson W.; Fuller, Christopher C.

    1998-01-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/λs, of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/λh= 2.6 hours), and in laboratory batch experiments using streambed sediment (1/λ = 2.7 hours). The modeled depths of subsurface storage zones (ds = 4–17 cm) and modeled residence times of water in storage zones (ts = 3–12 min) were both consistent with direct measurements in hyporheic flow paths (dh = 0–15 cm, th = 1–25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (fs = 8.9%, andfh = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The

  15. Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

    Science.gov (United States)

    Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

    2018-05-01

    Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

  16. The seasonal cycle and interannual variability of surface energy balance and melt in the ablation zone of the west Greenland ice sheet

    NARCIS (Netherlands)

    van den Broeke, M.R.; Smeets, C.J.P.P.; van de Wal, R.S.W.

    2011-01-01

    We present the seasonal cycle and interannual variability of the surface energy balance (SEB) in the ablation zone of the west Greenland ice sheet, using seven years (September 2003–August 2010) of hourly observations from three automatic weather stations (AWS). The AWS are situated along the 67◦ N

  17. Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

    Science.gov (United States)

    Lobo-Lapidus, Rodrigo J; Gates, Bruce C

    2010-10-04

    Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

  18. Reaction behavior of SO2 in the sintering process with flue gas recirculation.

    Science.gov (United States)

    Yu, Zhi-Yuan; Fan, Xiao-Hui; Gan, Min; Chen, Xu-Ling; Chen, Qiang; Huang, Yun-Song

    2016-07-01

    The primary goal of this paper is to reveal the reaction behavior of SO2 in the sinter zone, combustion zone, drying-preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO2 retention in the sinter zone was associated with free-CaO in the form of CaSO3/CaSO4, and the SO2 adsorption reached a maximum under 900ºC. SO2 in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO2 adsorption in the sintering bed mainly occurred in the drying-preheating zone, adsorbed by CaCO3, Ca(OH)2, and CaO. When the SO2 adsorption reaction in the drying-preheating zone reached equilibrium, the excess SO2 gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)2 and H2O. The emission rising point of SO2 moved forward in combustion zone, and the concentration of SO2 emissions significantly increased in the case of flue gas recirculation (FGR) technique. Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO2 emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO2 emissions because it will directly influence the demand and design of the FGD system.

  19. Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

    International Nuclear Information System (INIS)

    Rissmann, Clinton; Christenson, Bruce; Werner, Cynthia; Leybourne, Matthew; Cole, Jim; Gravley, Darren

    2012-01-01

    Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW e ). Soil CO 2 degassing was quantified with 2663 CO 2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m −2 ) using published soil temperature heat flow functions. Both CO 2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO 2 emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO 2 emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they

  20. Radially converging tracer test in a low-angle fracture zone at the Finnsjoen site, central Sweden. The fracture zone project - phase 3

    International Nuclear Information System (INIS)

    Gustafsson, E.; Nordqvist, R.

    1993-10-01

    The performance and results of a radially converging tracer test in a low-angle major fracture zone in crystalline rock are described. The extensive, about 100 m thick, zone 2 was encountered by means of borehole investigations at depths ranging from 100 to 250 metres at the Finnsjon site, central eastern Sweden. The zone studied (zone 2) consists of highly conductive, metre thick interconnected minor shear and fracture zones (sub-zones) with low conductive rock in between. The objective of the tracer test was primarily to determine flow and transport characteristics in a major fracture zone. Secondly new equipment, experimental design and methods of interpretation were developed, tested and improved. The converging flow field was created by pumping in a central borehole from a packed-off interval enclosing the whole thickness of zone 2. Tracer breakthrough was registered from all nine injection points, with first arrivals ranging from 24 to 3200 hours. Evaluated flow and transport parameters included; flow porosity, dispersivity, flow wetted surface, fracture aperture and hydraulic conductivity in fracture flow paths. Directional variations were found in the flow and transport parameters determined, which is concluded to be due to heterogeneity and/or anisotropy. This conditions is more pronounced at depth in zone 2. The results from the tracer test also clearly show that the upper boundary of zone 2 is highly conductive and consistent over hundreds of metres. Within zone 2, and between upper and lower margins, interconnected discrete minor shear and fracture zones (sub-zones) constitute flow paths of considerable variable residence times. The dispersion within the sub-zones of zone 2, expressed as Peclet numbers ranged from 16 to 40. Flow porosity was determined to be 0.001-0.05 in the upper sub-zone and 0.01-0.1 in the intermediate and lower ones and flow wetted surface area per volume of rock was calculated to be within 1-92 m 2 /m 3 . 68 refs, 61 figs, 40 tabs

  1. Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

    Science.gov (United States)

    Meyer, Jörg; Reuter, Karsten

    2014-04-25

    We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High rates of organic carbon processing in the hyporheic zone of intermittent streams.

    Science.gov (United States)

    Burrows, Ryan M; Rutlidge, Helen; Bond, Nick R; Eberhard, Stefan M; Auhl, Alexandra; Andersen, Martin S; Valdez, Dominic G; Kennard, Mark J

    2017-10-16

    Organic carbon cycling is a fundamental process that underpins energy transfer through the biosphere. However, little is known about the rates of particulate organic carbon processing in the hyporheic zone of intermittent streams, which is often the only wetted environment remaining when surface flows cease. We used leaf litter and cotton decomposition assays, as well as rates of microbial respiration, to quantify rates of organic carbon processing in surface and hyporheic environments of intermittent and perennial streams under a range of substrate saturation conditions. Leaf litter processing was 48% greater, and cotton processing 124% greater, in the hyporheic zone compared to surface environments when calculated over multiple substrate saturation conditions. Processing was also greater in more saturated surface environments (i.e. pools). Further, rates of microbial respiration on incubated substrates in the hyporheic zone were similar to, or greater than, rates in surface environments. Our results highlight that intermittent streams are important locations for particulate organic carbon processing and that the hyporheic zone sustains this fundamental process even without surface flow. Not accounting for carbon processing in the hyporheic zone of intermittent streams may lead to an underestimation of its local ecological significance and collective contribution to landscape carbon processes.

  3. Forests tend to cool the land surface in the temperate zone: An analysis of the mechanisms controlling radiometric surface temperature change in managed temperate ecosystems

    Science.gov (United States)

    Stoy, P. C.; Katul, G. G.; Juang, J.; Siqueira, M. B.; Novick, K. A.; Essery, R.; Dore, S.; Kolb, T. E.; Montes-Helu, M. C.; Scott, R. L.

    2010-12-01

    Vegetation is an important control on the surface energy balance and thereby surface temperature. Boreal forests and arctic shrubs are thought to warm the land surface by absorbing more radiation than the vegetation they replace. The surface temperatures of tropical forests tend to be cooler than deforested landscapes due to enhanced evapotranspiration. The effects of reforestation on surface temperature change in the temperate zone is less-certain, but recent modeling efforts suggest forests have a global warming effect. We quantified the mechanisms driving radiometric surface changes following landcover changes using paired ecosystem case studies from the Ameriflux database with energy balance models of varying complexity. Results confirm previous findings that deciduous and coniferous forests in the southeastern U.S. are ca. 1 °C cooler than an adjacent field on an annual basis because aerodynamic/ecophysiological cooling of 2-3 °C outweighs an albedo-related warming of stand-replacing ponderosa pine fire was ca. 1 °C warmer than unburned stands because a 1.5 °C aerodynamic warming offset a slight surface cooling due to greater albedo and soil heat flux. An ecosystem dominated by mesquite shrub encroachment was nearly 2 °C warmer than a native grassland ecosystem as aerodynamic and albedo-related warming outweighed a small cooling effect due to changes in soil heat flux. The forested ecosystems in these case studies are documented to have higher carbon uptake than the non-forested systems. Results suggest that temperate forests tend to cool the land surface and suggest that previous model-based findings that forests warm the Earth’s surface globally should be reconsidered.Changes to radiometric surface temperature (K) following changes in vegetation using paired ecosystem case studies C4 grassland and shrub ecosystem surface temperatures were adjusted for differences in air temperature across sites.

  4. Numerical simulation of porous burners and hole plate surface burners

    Directory of Open Access Journals (Sweden)

    Nemoda Stevan

    2004-01-01

    Full Text Available In comparison to the free flame burners the porous medium burners, especially those with flame stabilization within the porous material, are characterized by a reduction of the combustion zone temperatures and high combustion efficiency, so that emissions of pollutants are minimized. In the paper the finite-volume numerical tool for calculations of the non-isothermal laminar steady-state flow, with chemical reactions in laminar gas flow as well as within porous media is presented. For the porous regions the momentum and energy equations have appropriate corrections. In the momentum equations for the porous region an additional pressure drop has to be considered, which depends on the properties of the porous medium. For the heat transfer within the porous matrix description a heterogeneous model is considered. It treats the solid and gas phase separately, but the phases are coupled via a convective heat exchange term. For the modeling of the reaction of the methane laminar combustion the chemical reaction scheme with 164 reactions and 20 chemical species was used. The proposed numerical tool is applied for the analyses of the combustion and heat transfer processes which take place in porous and surface burners. The numerical experiments are accomplished for different powers of the porous and surface burners, as well as for different heat conductivity character is tics of the porous regions.

  5. Final Report Theoretical Studies of Surface Reactions on Metals and Electronic Materials

    Energy Technology Data Exchange (ETDEWEB)

    Jerry L. Whitten

    2012-04-23

    This proposal describes the proposed renewal of a theoretical research program on the structure and reactivity of molecules adsorbed on transition metal surfaces. A new direction of the work extends investigations to interfaces between solid surfaces, adsorbates and aqueous solutions and includes fundamental work on photoinduced electron transport into chemisorbed species and into solution. The goal is to discover practical ways to reduce water to hydrogen and oxygen using radiation comparable to that available in the solar spectrum. The work relates to two broad subject areas: photocatalytic processes and production of hydrogen from water. The objective is to obtain high quality solutions of the electronic structure of adsorbate-metal-surface-solution systems so as to allow activation barriers to be calculated and reaction mechanisms to be determined. An ab initio embedding formalism provides a route to the required accuracy. New theoretical methods developed during the previous grant period will be implemented in order to solve the large systems involved in this work. Included is the formulation of a correlation operator that is used to treat localized electron distributions such as ionic or regionally localized distributions. The correlation operator which is expressed as a two-particle projector is used in conjunction with configuration interaction.

  6. Small-scale spatial variability of phenoxy acid mineralization potentials in transition zones with a multidisciplinary approach

    DEFF Research Database (Denmark)

    Pazarbasi, Meric Batioglu

    The phenoxy acid group of herbicides is widely used to control broadleaf weeds, and it contaminates groundwater and surface water by leaching from agricultural soil or landfills. Due to the distinct vertical and horizontal gradients in nutrients and hydrologic exchange in transition zones...... in two transition zones, (1) the interfaces of unsaturated and saturated zones and (2) groundwater and surface water. Small-scale spatial variability of phenoxy acids was previously shown in topsoil; however, such small-scale studies are scarce in subsurface environments. We therefore studied the factors...... classes in the different mineralization potentials of discharge zones. Understanding of the natural attenuation potential of groundwater-surface water transition zones is important for stream water protection. In landfill-impacted groundwater-surface water interface, we further analyzed bacterial...

  7. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2007-05-15

    Pressed graphite felt (thickness {proportional_to}350 {mu}m) with electrodeposited PtRu (43 g m{sup -2}, 1.4:1 atomic ratio) or PtRuMo (52 g m{sup -2}, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m{sup -2} with PtRuMo at 5500 A m{sup -2} and 353 K while under the same conditions PtRu yielded 1925 W m{sup -2}. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation. (author)

  8. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Science.gov (United States)

    Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

    Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

  9. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    Science.gov (United States)

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-10-01

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

  10. Dynamics of the transition zone in coastal zone color scanner-sensed ocean color in the North Pacific during oceanographic spring

    Science.gov (United States)

    Glover, David M.; Wroblewski, J. S.; Mcclain, Charles R.

    1994-01-01

    A transition zone in phytoplankton concentration running across the North Pacific basin at 30 deg to 40 deg north latitude corresponds to a basin-wide front in surface chlorophyll observed in a composite of coastal zone color scanner (CZCS) images for May, June, and July 1979-1986. This transition zone with low chlorophyll to the south and higher chlorophyll to the north can be simulated by a simple model of the concentration of phytoplankton, zooplankton, and dissolved nutrient (nitrate) in the surface mixed layer of the ocean applied to the North Pacific basin for the climatological conditions during oceanographic springtime (May, June, and July). The model is initialized with a 1 deg x 1 deg gridded estimate of wintertime (February, March, and April) mixed layer nitrate concentrations calculated from an extensive nutrient database and a similarly gridded mixed layer depth data set. Comparison of model predictions with CZCS data provides a means of evaluating the dynamics of the transition zone. We conclude that in the North Pacific, away from major boundary currents and coastal upwelling zones, wintertime vertical mixing determines the total nutrient available to the plankton ecosystem in the spring. The transition zone seen in basin-scale CZCS images is a reflection of the geographic variation in the wintertime mixed layer depth and the nitracline, leading to a latitudinal gradient in phytoplankton chlorophyll.

  11. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  12. Dynamics and mitigation of six pesticides in a "Wet" forest buffer zone.

    Science.gov (United States)

    Passeport, Elodie; Richard, Benjamin; Chaumont, Cédric; Margoum, Christelle; Liger, Lucie; Gril, Jean-Joël; Tournebize, Julien

    2014-04-01

    Pesticide pollution is one of the main current threats on water quality. This paper presents the potential and functioning principles of a "Wet" forest buffer zone for reducing concentrations and loads of glyphosate, isoproturon, metazachlor, azoxystrobin, epoxiconazole, and cyproconazole. A tracer injection experiment was conducted in the field in a forest buffer zone at Bray (France). A fine time-scale sampling enabled to illustrate that interactions between pesticides and forest buffer substrates (soil and organic-rich litter layer), had a retarding effect on molecule transfer. Low concentrations were observed for all pesticides at the forest buffer outlet thus demonstrating the efficiency of "Wet" forest buffer zone for pesticide dissipation. Pesticide masses injected in the forest buffer inlet directly determined concentration peaks observed at the outlet. Rapid and partially reversible adsorption was likely the major process affecting pesticide transfer for short retention times (a few hours to a few days). Remobilization of metazachlor, isoproturon, desmethylisoproturon, and AMPA was observed when non-contaminated water flows passed through the forest buffer. Our data suggest that pesticide sorption properties alone could not explain the complex reaction mechanisms that affected pesticide transfer in the forest buffer. Nevertheless, the thick layer of organic matter litter on the top of the forest soil was a key parameter, which enhanced partially reversible sorption of pesticide, thus retarded their transfer, decreased concentration peaks, and likely increased degradation of the pesticides. Consequently, to limit pesticide pollution transported by surface water, the use of already existing forest areas as buffer zones should be equally considered as the most commonly implemented grass buffer strips.

  13. Research project AUS-10370/CF: electron impact ionization and surface induced reactions of edge plasma constituents

    International Nuclear Information System (INIS)

    Maerk, T.D.

    1999-01-01

    In order to better understand elementary reactions which are taking place at the plasma edge of thermonuclear fusion devices, three areas of research were persuaded: I) Experimental studies about electron ionization of neutrals and ions and electron attachment to molecules, II) Theoretical studies about electron ionisation of neutrals and ions and III) Reactive interaction of molecular ions with surfaces

  14. The acid-base resistant zone in three dentin bonding systems.

    Science.gov (United States)

    Inoue, Go; Nikaido, Toru; Foxton, Richard M; Tagami, Junji

    2009-11-01

    An acid-base resistant zone has been found to exist after acid-base challenge adjacent to the hybrid layer using SEM. The aim of this study was to examine the acid-base resistant zone using three different bonding systems. Dentin disks were applied with three different bonding systems, and then a resin composite was light-cured to make dentin disk sandwiches. After acid-base challenge, the polished surfaces were observed using SEM. For both one- and two-step self-etching primer systems, an acid-base resistant zone was clearly observed adjacent to the hybrid layer - but with differing appearances. For the wet bonding system, the presence of an acid-base resistant zone was unclear. This was because the self-etching primer systems etched the dentin surface mildly, such that the remaining mineral phase of dentin and the bonding agent yielded clear acid-base resistant zones. In conclusion, the acid-base resistant zone was clearly observed when self-etching primer systems were used, but not so for the wet bonding system.

  15. Oxygen 18 concentration profile measurements near the surface by 18O(p,α)15N resonance reaction

    International Nuclear Information System (INIS)

    Amsel, G.; David, D.

    1975-01-01

    The method of spectrum reduction in nuclear reaction microanalysis does not allow to obtain depth resolutions better than the order of 2000A. Resolutions of the order of 200A may be obtained by using the narrow resonance technique, when applied to thin films. The latter technique was extended to thick targets, with deep concentration profiles presenting a sharp gradient near the surface. This method is presented and illustrated by the study of 18 O profiles in oxygen diffusion measurements in growing ZrO 2 , using the 629keV resonance of the reaction 18 O(p,α) 15 N [fr

  16. A Monte Carlo simulation of the exchange reaction between gaseous molecules and the atoms on a heterogeneous solid surface

    International Nuclear Information System (INIS)

    Imai, Hisao

    1980-01-01

    A method of the Monte Carlo simulation of the isotopic exchange reaction between gaseous molecules and the atoms on an arbitrarily heterogeneous solid surface is described by employing hydrogen as an example. (author)

  17. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

    2016-12-05

    Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

  18. Transforming growth factor β-induced superficial zone protein accumulation in the surface zone of articular cartilage is dependent on the cytoskeleton.

    Science.gov (United States)

    McNary, Sean M; Athanasiou, Kyriacos A; Reddi, A Hari

    2014-03-01

    The phenotype of articular chondrocytes is dependent on the cytoskeleton, specifically the actin microfilament architecture. Articular chondrocytes in monolayer culture undergo dedifferentiation and assume a fibroblastic phenotype. This process can be reversed by altering the actin cytoskeleton by treatment with cytochalasin. Whereas dedifferentiation has been studied on chondrocytes isolated from the whole cartilage, the effects of cytoskeletal alteration on specific zones of cells such as superficial zone chondrocytes are not known. Chondrocytes from the superficial zone secrete superficial zone protein (SZP), a lubricating proteoglycan that reduces the coefficient of friction of articular cartilage. A better understanding of this phenomenon may be useful in elucidating chondrocyte dedifferentiation in monolayer and accumulation of the cartilage lubricant SZP, with an eye toward tissue engineering functional articular cartilage. In this investigation, the effects of cytoskeletal modulation on the ability of superficial zone chondrocytes to secrete SZP were examined. Primary superficial zone chondrocytes were cultured in monolayer and treated with a combination of cytoskeleton modifying reagents and transforming growth factor β (TGFβ) 1, a critical regulator of SZP production. Whereas cytochalasin D maintains the articular chondrocyte phenotype, the hallmark of the superficial zone chondrocyte, SZP, was inhibited in the presence of TGFβ1. A decrease in TGFβ1-induced SZP accumulation was also observed when the microtubule cytoskeleton was modified using paclitaxel. These effects of actin and microtubule alteration were confirmed through the application of jasplakinolide and colchicine, respectively. As Rho GTPases regulate actin organization and microtubule polymerization, we hypothesized that the cytoskeleton is critical for TGFβ-induced SZP accumulation. TGFβ-mediated SZP accumulation was inhibited by small molecule inhibitors ML141 (Cdc42), NSC23766 (Rac1

  19. MAPPING LOCAL CLIMATE ZONES WITH A VECTOR-BASED GIS METHOD

    Directory of Open Access Journals (Sweden)

    E. Lelovics

    2013-03-01

    Full Text Available In this study we determined Local Climate Zones in a South-Hungarian city, using vector-based and raster-based databases. We calculated seven of the originally proposed ten physical (geometric, surface cover and radiative properties for areas which are based on the mobile temperature measurement campaigns earlier carried out in this city.As input data we applied 3D building database (earlier created with photogrammetric methods, 2D road database, topographic map, aerial photographs, remotely sensed reflectance information from RapidEye satellite image and our local knowledge about the area. The values of the properties were calculated by GIS methods developed for this purpose.We derived for the examined areas and applied for classification sky view factor, mean building height, terrain roughness class, building surface fraction, pervious surface fraction, impervious surface fraction and albedo.Six built and one land cover LCZ classes could be detected with this method on our study area. From each class one circle area was selected, which is representative for that class. Their thermal reactions were examined with the application of mobile temperature measurement dataset. The comparison was made in cases, when the weather was clear and calm and the surface was dry. We found that compact built-in types have more temperature surplus than open ones, and midrise types also have more than lowrise ones. According to our primary results, these categories provide a useful opportunity for intra- and inter-urban comparisons.

  20. A nonsteady-state firn-densification model for the percolation zone of a glacier

    DEFF Research Database (Denmark)

    Reeh, Niels

    2008-01-01

    A simple steady state firn-densification model is modified to account for short-term time variations of accumulation rate and surface temperature. The temporal surface-elevation- and mass changes at two sites in the percolation zone of an ice sheet in response to various climate histories...... are determined. It is shown that a straight-forward translation of observed short-term ice-sheet surface-elevation variations into mass changes may be completely misleading, particularly for the percolation zone of the ice sheet, where temperature driven variations of melting/re-freezing rates have a strong...... impact on near surface density. In the lower percolation zone, the mass change associated with a temperature anomaly in respect to the mean climate may for example amount to as little as 10 percent of the observed, simultaneous surface elevation change. Moreover, significant surface elevation change may...

  1. An ab initio potential energy surface for the reaction N+ + H2→ NH+ + H

    International Nuclear Information System (INIS)

    Gittins, M.A.; Hirst, D.M.

    1975-01-01

    Preliminary results of ab initio unrestricted Hartree-Fock calculations for the potential energy surface for the reaction N + + H 2 →NH + + H are reported. For the collinear approach of N + to H 2 , the 3 Σ - surface has no activation barrier and has a shallow well (ca.1eV). For perpendicular approach (Csub(2V)symmetry) the 3 B 2 states is of high energy, the 3 A 2 state has a shallow well but as the bond angle increases the 3 B 1 states decreases in energy to become the state of lowest energy. Neither the collinear nor the perpendicular approaches give adiabatic pathways to the deep potential well of 3 B 1 (HNH) + . (auth.)

  2. Radioactivity in the Exclusive Economic Zone of east coast Peninsular Malaysia. Distribution trends of 137Cs in surface seawater

    International Nuclear Information System (INIS)

    Zaharudin Ahmad; Zal U'yun Wan Mahmood; Hidayah Shahar; Mei Wo Yii; Ahmad Sanadi Abu Bakar

    2011-01-01

    Large volumes of surface seawater samples were collected from thirty locations in the Exclusive Economic Zone (EEZ) of the east coast Peninsular Malaysia on June 2008 to study the activity concentrations of 137 Cs. The results will serve as additional information to the existing baseline data and is very useful for monitoring fresh input of anthropogenic radionuclide into Malaysian marine environment. In this study, the activity concentrations of 137 Cs were determined using co-precipitation technique, followed by Gamma Spectrometry measurement. The mean activity concentration of 137 Cs ranged between 3.40 and 5.89 Bq/m 3 . Higher activity concentrations were observed at the coastal and towards the south of Peninsular Malaysia and were aligned with the high turbidity. These may due to the rapid diffusion of 137 Cs from suspended particulates and fine sediments into surface seawater. The activity concentrations of 137 Cs observed in this study were slightly higher than the concentrations reported in seawater at the Straits of Malacca, Vietnam and Philippines. This might be because the study area received more input of 137 Cs that originated from global fallout and then deposited on land which later being transported subsequently into the coastal zone due to siltation and erosion processes. It could also be attributed to the intrusion of river waters containing higher concentrations of 137 Cs. (author)

  3. Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

    Science.gov (United States)

    Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

    2006-01-01

    Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

  4. Probing the rate-determining region of the potential energy surface for a prototypical ion-molecule reaction.

    Science.gov (United States)

    Xie, Changjian; Liu, Xinguo; Sweeny, Brendan C; Miller, Thomas M; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

    2018-03-13

    We report a joint experimental-theoretical study of the F -  + HCl → HF + Cl - reaction kinetics. The experimental measurement of the rate coefficient at several temperatures was made using the selected ion flow tube method. Theoretical rate coefficients are calculated using the quasi-classical trajectory method on a newly developed global potential energy surface, obtained by fitting a large number of high-level ab initio points with augmentation of long-range electrostatic terms. In addition to good agreement between experiment and theory, analyses suggest that the ion-molecule reaction rate is significantly affected by shorter-range interactions, in addition to the traditionally recognized ion-dipole and ion-induced dipole terms. Furthermore, the statistical nature of the reaction is assessed by comparing the measured and calculated HF product vibrational state distributions to that predicted by the phase space theory.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  5. Proton-transfer reactions in ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.; Schmidt, R.; Schuster, R.

    1985-01-01

    Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

  6. Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. II. Photoelectron spectroscopy and microscopy

    Science.gov (United States)

    Smolinsky, Tim; Homann, Mathias; von Boehn, Bernhard; Gregoratti, Luca; Amati, Matteo; Al-Hada, Mohamed; Sezen, Hikmet; Imbihl, Ronald

    2018-04-01

    Chemical waves in the H2 + O2 reaction on a Rh(111) surface alloyed with Ni [ΘNi chemical attraction between O and Ni, has been explained with a phase separation of the oxygen covered Rh(111)/Ni surface into a 3D-Ni oxide and into a Ni poor metallic phase. Macroscopic NiO islands (≈1 μm size) formed under reaction conditions have been identified as 2D-Ni oxide. Titration experiments of the oxygen covered Rh(111)/Ni surface with H2 demonstrated that the reactivity of oxygen is decreased by an order of magnitude through the addition of 0.6 ML Ni. An excitation mechanism is proposed in which the periodic formation and reduction of NiO modulate the catalytic activity.

  7. Corrosion of ferritic steels by molten lithium: Influence of competing thermal gradient mass transfer and surface product reactions

    International Nuclear Information System (INIS)

    Tortorelli, P.F.

    1987-10-01

    An Fe-12Cr-1MoVW steel was exposed to thermally convective lithium for 6962 h. Results showed that the weight change profile of Fe-12Cr-1MoVW steel changed substantially as the maximum loop temperature was raised from 500 to 600 0 C. Furthermore, for a particular loop experiment, changes in the structure and composition of the exposed surfaces did not reflect typical thermal gradient mass transfer effects for all elements: the surface concentration of chromium was often a maximum at intermediate temperatures, while nickel (present at low concentrations in the starting material) tended to be transported to the coldest part of the loop. Such data were interpreted in terms of a qualitative model in which there are different dominant reactions or the various constituents of the ferritic steels (surface product formation involving nitrogen and/or carbon and solubility-driven elemental transport). This competition among different reactions is important in evaluating overall corrosion behavior and the effects of temperature. The overall corrosion rate of the 12Cr-1MoVW steel was relatively low when compared to that for austenitic stainless steel exposed under similar conditions

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

    Science.gov (United States)

    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.

  9. Quantification of Fault-Zone Plasticity Effects with Spontaneous Rupture Simulations

    Science.gov (United States)

    Roten, D.; Olsen, K. B.; Day, S. M.; Cui, Y.

    2017-09-01

    Previous studies have shown that plastic yielding in crustal rocks in the fault zone may impose a physical limit to extreme ground motions. We explore the effects of fault-zone non-linearity on peak ground velocities (PGVs) by simulating a suite of surface-rupturing strike-slip earthquakes in a medium governed by Drucker-Prager plasticity using the AWP-ODC finite-difference code. Our simulations cover magnitudes ranging from 6.5 to 8.0, three different rock strength models, and average stress drops of 3.5 and 7.0 MPa, with a maximum frequency of 1 Hz and a minimum shear-wave velocity of 500 m/s. Friction angles and cohesions in our rock models are based on strength criteria which are frequently used for fractured rock masses in civil and mining engineering. For an average stress drop of 3.5 MPa, plastic yielding reduces near-fault PGVs by 15-30% in pre-fractured, low strength rock, but less than 1% in massive, high-quality rock. These reductions are almost insensitive to magnitude. If the stress drop is doubled, plasticity reduces near-fault PGVs by 38-45% and 5-15% in rocks of low and high strength, respectively. Because non-linearity reduces slip rates and static slip near the surface, plasticity acts in addition to, and may partially be emulated by, a shallow velocity-strengthening layer. The effects of plasticity are exacerbated if a fault damage zone with reduced shear-wave velocities and reduced rock strength is present. In the linear case, fault-zone trapped waves result in higher near-surface peak slip rates and ground velocities compared to simulations without a low-velocity zone. These amplifications are balanced out by fault-zone plasticity if rocks in the damage zone exhibit low-to-moderate strength throughout the depth extent of the low-velocity zone (˜5 km). We also perform dynamic non-linear simulations of a high stress drop (8 MPa) M 7.8 earthquake rupturing the southern San Andreas fault along 250 km from Indio to Lake Hughes. Non-linearity in the

  10. [Cytostructure of the mantle zone in lymphatic tissue].

    Science.gov (United States)

    Bednár, B

    1993-04-01

    Four cellular layers of the follicular mantle zone in palatine tonsil lymphatic tissue were studied by electron microscopy after simultaneous immunophenotypical investigation. The first layer of the mantle zone consisting of small blastic cells was analogous to the small (centrocytoid) blastic layer of germinal centres. The second B monocytoid layer was lacking analogy in basic series of lymphocytes and seemed to be an independent morphological and probably functional unit. Plasmacytoid and clarocellular elements in outer layers of follicular mantle zone were in a way similar to T plasmacytoid and clarocellular components of Sézary syndrome infiltrates but considering transitional forms they had a local origin from incompletely transformed elements of B monocytoid layer. Inner follicular mantle zone was discussed as a source of incompletely transformed B lymphocytes for further mantle layers where their immunophenotypical modulation is taking place according to actual need. Outer mantle layers are aggressive against damaged epithelial and litoral structures and may be instrumental in a common reaction of B and T components.

  11. Adsorption and diffusion of H and NH{sub x} as key steps of the NH{sub x} dehydrogenation reaction at the V{sub 2}O{sub 5} (010) surface

    Energy Technology Data Exchange (ETDEWEB)

    Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, und Sfb 546, Berlin (Germany)

    2009-07-01

    Various selective oxidation reactions as the selective catalytic reduction (SCR) of NO{sub x} or the ammoxidation of propane/propene to acrylonitrile are processed on vanadium based metal-oxide catalysts in the presence of ammonia. In the reactions the intermediates NH{sub 2}, NH{sub 3}, and NH{sub 4} are involved indicating that the adsorption and dehydrogenation of NH{sub x}, x < 4, are important steps. We have performed theoretical studies of corresponding reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5} (010) surface. The calculations apply density-functional theory combined with clusters modeling the adsorbate system. The substrate lowers corresponding dehydrogenation energies considerably compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation of NH{sub 3} likely to happen. Our results on the role of oxygen vacancies for the dehydrogenation indicate that such surface defects become important for the reaction. Besides the energetics also the diffusion at the surface influences the reaction. A nudged elastic band (NEB) routine has been implemented to evaluate diffusion paths and barriers. Hydrogen diffusion on the surface will be discussed and additional examples for NH{sub x} diffusion will be shown. Based on these results possible reaction scenarios for the dehydrogenation reaction will be presented.

  12. Stagnant zone formation on diamond cutting tools during machining

    International Nuclear Information System (INIS)

    Izman, S.; Tamin, M.N.; Mon, T.T.; Venkatesh, V.C.; Shaharoun, A.M.

    2007-01-01

    Formation of an intact region on the rake face of cutting tool during machining is quite common phenomenon but its significance in maintaining tool edge sharpness has not been recognized by many researchers. This region is sometimes called stagnant zone. It is believed that when an intact zone present on the rake face, it delays the crater wear progress and hence maintaining the tool edge sharpness longer. This paper investigates the effect of edge radius, surface roughness of the rake face and cutting parameters on the formation of stagnant zone on two different type of diamond tools i.e. polycrystalline diamond PCD-KD100 and diamond-coated inserts when machining titanium alloy. The used inserta and post-processed chips were examined under FESEM and optical microscope after cutting at three different conditions. Experimental results show that the speed and feel, the tool edge radius, and the tool rake surface roughness significantly affect the stagnant zone formation. (author)

  13. MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL

    2013-11-14

    The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in the subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.

  14. Efficient Computational Research Protocol to Survey Free Energy Surface for Solution Chemical Reaction in the QM/MM Framework: The FEG-ER Methodology and Its Application to Isomerization Reaction of Glycine in Aqueous Solution.

    Science.gov (United States)

    Takenaka, Norio; Kitamura, Yukichi; Nagaoka, Masataka

    2016-03-03

    In solution chemical reaction, we often need to consider a multidimensional free energy (FE) surface (FES) which is analogous to a Born-Oppenheimer potential energy surface. To survey the FES, an efficient computational research protocol is proposed within the QM/MM framework; (i) we first obtain some stable states (or transition states) involved by optimizing their structures on the FES, in a stepwise fashion, finally using the free energy gradient (FEG) method, and then (ii) we directly obtain the FE differences among any arbitrary states on the FES, efficiently by employing the QM/MM method with energy representation (ER), i.e., the QM/MM-ER method. To validate the calculation accuracy and efficiency, we applied the above FEG-ER methodology to a typical isomerization reaction of glycine in aqueous solution, and reproduced quite satisfactorily the experimental value of the reaction FE. Further, it was found that the structural relaxation of the solute in the QM/MM force field is not negligible to estimate correctly the FES. We believe that the present research protocol should become prevailing as one computational strategy and will play promising and important roles in solution chemistry toward solution reaction ergodography.

  15. Dehydration-driven topotaxy in subduction zones

    Science.gov (United States)

    Padrón-Navarta, José Alberto; Tommasi, Andréa; Garrido, Carlos J.

    2014-05-01

    Mineral replacement reactions play a fundamental role in the chemistry and the strength of the lithosphere. When externally or internally derived fluids are present, interface-coupled dissolution-precipitation is the driving mechanism for such reactions [1]. One of the microstructural features of this process is a 3D arrangement of crystallographic axes across internal interfaces (topotaxy) between reactant and product phases. Dehydration reactions are a special case of mineral replacement reaction that generates a transient fluid-filled porosity. Among others, the dehydration serpentinite is of special relevance in subduction zones because of the amount of fluids involved (potentially up to 13 wt.%). Two topotatic relationships between olivine and antigorite (the serpentine mineral stable at high temperature and pressure) have been reported in partially hydrated mantle wedge xenoliths [2]. Therefore, if precursor antigorite serpentine has a strong crystallographic preferred orientation (CPO) its dehydration might result in prograde peridotite with a strong inherited CPO. However for predicting the importance of topotactic reactions for seismic anisotropy of subduction zones we also need to consider the crystallization orthopyroxene + chlorite in the prograde reaction and, more importantly, the fact that this dehydration reaction produces a transient porosity of ca. 20 % vol. that results in local fluctuations of strain during compaction and fluid migration. We address this issue by a microstructural comparison between the CPO developed in olivine, orthopyroxene and chlorite during high-pressure antigorite dehydration in piston cylinder experiments (at 750ºC and 20 kbar and 1000ºC and 30 kbar, 168 h) and that recorded in natural samples (Cerro del Almirez, Betic Cordillera, Spain). Experimentally developed CPOs are strong. Prograde minerals show a significant inheritance of the former antigorite foliation. Topotactic relations are dominated by (001)atg//(100)ol

  16. Reactions between Ti3Al-Nb and mixed second phases

    International Nuclear Information System (INIS)

    Bowden, D.M.; Sastry, S.M.L.; Smith, P.R.

    1989-01-01

    In engineered multiphase materials, the interfacial characteristics that develop between individual phases during high-temperature exposure can play a significant role in determining mechanical behavior. In titanium alloys containing silicon carbide and boron fibers, rule-of-mixtures strength values are not realized, primarily because of the chemical reactions that occur between the matrix alloys and these phases. Previous investigations of the reaction between titanium alloys and boron have shown that a uniform reaction layer of the phase TiB 2 is formed, followed by growth of TiB needles. The primary mechanism of this reaction was observed to be the one-way diffusion of boron into titanium. The use of a B 4 C coating on the boron (B 4 C/B) as a diffusion barrier was found to significantly slow the reaction between the titanium and boron. Certain alloy additions to titanium, such as aluminum, vanadium, and molybdenum, can increase the chemical compatibility of these two phases. For the case of SiC, the reaction zone is formed by the interdiffusion of silicon and carbon atoms with titanium. X-ray diffraction studies have shown the reaction components to include TiC, Ti 5 Si 3 , and TiSi 2 . In the present study, the reactions between a Ti 3 Al alloy and both B 4 C/B and SiC have been examined. Reaction models are proposed to describe the development of the chemical interaction zone formed between these phases

  17. Denitrifiers in the surface zone are primarily responsible for the nitrous oxide emission of dairy manure compost

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, Koki, E-mail: k_maeda@affrc.go.jp [Dairy Research Division, National Agricultural Research Center for Hokkaido Region, National Agricultural and Food Research Organization, 1 Hitsujigaoka, Sapporo 062-8555 (Japan); Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Toyoda, Sakae [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Hanajima, Dai [Dairy Research Division, National Agricultural Research Center for Hokkaido Region, National Agricultural and Food Research Organization, 1 Hitsujigaoka, Sapporo 062-8555 (Japan); Yoshida, Naohiro [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2013-03-15

    Highlights: ► Nitrous oxide (N{sub 2}O) productions of each compost zones were compared. ► The pile surface emitted significant fluxes of N{sub 2}O. ► The isotopic signature of N{sub 2}O from surface and NO{sub 2}{sup −} amended core were different. ► The denitrifying gene abundance was significantly higher in pile surface than the pile core. -- Abstract: During the dairy manure composting process, significant nitrous oxide (N{sub 2}O) emissions occur just after the pile turnings. To understand the characteristics of this N{sub 2}O emission, samples were taken from the compost surface and core independently, and the N{sub 2}O production was monitored in laboratory incubation experiments. Equal amounts of surface and core samples were mixed to simulate the turning, and the {sup 15}N isotope ratios within the molecules of produced N{sub 2}O were analyzed by isotopomer analysis. The results showed that the surface samples emitted significant levels of N{sub 2}O, and these emissions were correlated with NO{sub x}{sup −}-N accumulation. Moreover, the surface samples and surface-core mixed samples incubated at 30 °C produced N{sub 2}O with a low site preference (SP) value (−0.9 to 7.0‰) that was close to bacteria denitrification (0‰), indicating that denitrifiers in the surface samples are responsible for this N{sub 2}O production. On the other hand, N{sub 2}O produced by NO{sub 2}{sup −}-amended core samples and surface samples incubated at 60 °C showed unrecognized isotopic signatures (SP = 11.4–20.3‰). From these results, it was revealed that the N{sub 2}O production occurring just after the turnings was mainly derived from bacterial denitrification (including nitrifier denitrification) of NO{sub x}{sup −}-N under mesophilic conditions, and surface denitrifying bacteria appeared to be the main contributor to this process.

  18. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule to the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  19. Effect of high-extraction coal mining on surface and ground waters

    International Nuclear Information System (INIS)

    Kendorski, F.S.

    1993-01-01

    Since first quantified around 1979, much new data have become available. In examining the sources of data and the methods and intents of the researchers of over 65 case histories, it became apparent that the strata behaviors were being confused with overlapping vertical extents reported for the fractured zones and aquiclude zones depending on whether the researcher was interested in water intrusion into the mine or in water loss from surface or ground waters. These more recent data, and critical examination of existing data, have led to the realization that the former Aquiclude Zone defined for its ability to prevent or minimize the intrusion of ground or surface waters into mines has another important character in increasing storage of surface and shallow ground waters in response to mining with no permanent loss of waters. This zone is here named the Dilated Zone. Surface and ground waters can drain into this zone, but seldom into the mine, and can eventually be recovered through closing of dilations by mine subsidence progression away from the area, or filling of the additional void space created, or both. A revised model has been developed which accommodates the available data, by modifying the zones as follows: collapse and disaggregation extending 6 to 10 times the mined thickness above the panel; continuous fracturing extending approximately 24 times the mined thickness above the panel, allowing temporary drainage of intersected surface and ground waters; development of a zone of dilated, increased storativity, and leaky strata with little enhanced vertical permeability from 24 to 60 times the mined thickness above the panel above the continuous fracturing zone, and below the constrained or surface effects zones; maintenance of a constrained but leaky zone above the dilated zone and below the surface effects zone; and limited surface fracturing in areas of extension extending up to 50 ft or so beneath the ground surface. 119 ref., 5 figs., 2 tabs

  20. Phosphorus zoning as a recorder of crystal growth kinetics

    DEFF Research Database (Denmark)

    Baziotis, I.; Asimow, P.D.; Ntaflos, T.

    2017-01-01

    spectrometry. The petrogenetic history of each vein involves melt intrusion, cooling accompanied by both wall-rock reaction and crystallization, quench of melt to a glass, and possibly later modifications. Exotic secondary olivine crystals in the veins display concentric phosphorus (P)-rich zoning, P...

  1. The hydrogen abstraction reaction O(3P) + CH4: A new analytical potential energy surface based on fit to ab initio calculations

    International Nuclear Information System (INIS)

    González-Lavado, Eloisa; Corchado, Jose C.; Espinosa-Garcia, Joaquin

    2014-01-01

    Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system

  2. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

    KAUST Repository

    Muir, J. N.

    2012-01-01

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

  3. Hydrogeologic controls on the transport and fate of nitrate in ground water beneath riparian buffer zones: Results from thirteen studies across the United States

    Science.gov (United States)

    Puckett, L.J.

    2004-01-01

    During the last two decades there has been growing interest in the capacity of riparian buffer zones to remove nitrate from ground waters moving through them. Riparian zone sediments often contain organic carbon, which favors formation of reducing conditions that can lead to removal of nitrate through denitrification. Over the past decade the National Water Quality Assessment (NAWQA) Program has investigated the transport and fate of nitrate in ground and surface waters in study areas across the United States. In these studies riparian zone efficiency in removing nitrate varied widely as a result of variations in hydrogeologic factors. These factors include (1) denitrification in the up-gradient aquifer due to the presence of organic carbon or other electron donors, (2) long residence times (>50 years) along ground-water flow paths allowing even slow reactions to completely remove nitrate, (3) dilution of nitrate enriched waters with older water having little nitrate, (4) bypassing of riparian zones due to extensive use of drains and ditches, and (5) movement of ground water along deep flow paths below reducing zones. By developing a better understanding of the hydrogeologic settings in which riparian buffer zones are likely to be inefficient we can develop improved nutrient management plans. ?? US Government 2004.

  4. A broader classification of damage zones

    Science.gov (United States)

    Peacock, D. C. P.; Dimmen, V.; Rotevatn, A.; Sanderson, D. J.

    2017-09-01

    Damage zones have previously been classified in terms of their positions at fault tips, walls or areas of linkage, with the latter being described in terms of sub-parallel and synchronously active faults. We broaden the idea of linkage to include structures around the intersections of non-parallel and/or non-synchronous faults. These interaction damage zones can be divided into approaching damage zones, where the faults kinematically interact but are not physically connected, and intersection damage zones, where the faults either abut or cross-cut. The damage zone concept is applied to other settings in which strain or displacement variations are taken up by a range of structures, such as at fault bends. It is recommended that a prefix can be added to a wide range of damage zones, to describe the locations in which they formed, e.g., approaching, intersection and fault bend damage zone. Such interpretations are commonly based on limited knowledge of the 3D geometries of the structures, such as from exposure surfaces, and there may be spatial variations. For example, approaching faults and related damage seen in outcrop may be intersecting elsewhere on the fault planes. Dilation in intersection damage zones can represent narrow and localised channels for fluid flow, and such dilation can be influenced by post-faulting stress patterns.

  5. Analysis of surface roughness and surface heat affected zone of steel S355J0 after plasma arc cutting

    International Nuclear Information System (INIS)

    Hatala, Michal; Chep, Robert; Pandilov, Zoran

    2010-01-01

    This paper deals with thermal cutting technology of materials with plasma arc. In the first part of this paper the theoretical knowledge of the principles of plasma arc cutting and current use of this technology in industry are presented. The cut of products with this technology is perpendicular and accurate, but the use of this technology affects micro-structural changes and depth of the heat affected zone (HAZ). This article deals with the experimental evaluation of plasma arc cutting technological process. The influence of technological factors on the roughness parameter Ra of the steel surface EN S355J0 has been evaluated by using planned experiments. By using the factor experiment, the significance of the four process factors such as plasma burner feed speed, plasma gas pressure, nozzle diameter, distance between nozzle mouth and material has been analyzed. Regression models obtained by multiple linear regression indicate the quality level of observed factors function. The heat from plasma arc cutting affects the micro-structural changes of the material, too.

  6. How deep can surface signals be traced in the critical zone? Merging biodiversity with biogeochemistry research in a central German Muschelkalk landscape

    Directory of Open Access Journals (Sweden)

    Kirsten eKüsel

    2016-04-01

    Full Text Available The Earth’s Critical Zone (CZ is a thin living layer connecting atmosphere and geosphere, including aquifers. Humans live in the CZ and benefit from the vital supporting services it provides. However, the CZ is increasingly impacted by human activities including land and resource use, pollution and climate change. Recent interest in uniting the many disciplines studying this complex domain has initiated an international network of research infrastructure platforms that allow access to the CZ in a range of geologic settings. In this paper a new such infrastructure platform associated with the Collaborative Research Center AquaDiva is described, that uniquely seeks to combine CZ research with detailed investigation of the functional biodiversity of the subsurface. Overall, AquaDiva aims to test hypotheses about how water connects surface conditions set by land cover and land management to the biota and biogeochemical functions in the subsurface. With long-term and continuous observations, hypotheses about how seasonal variations and extreme events at the surface impact subsurface processes, community structure and function, are tested. AquaDiva has established the Hainich Critical Zone Exploratory (CZE in central Germany in an alkaline geological setting of German Triassic Muschelkalk formations. The Hainich CZE includes specialized monitoring wells to access the vadose zone and two main groundwater complexes in limestone and marlstone parent materials along a ~6 km transect spanning forest, pasture and agricultural land uses. Initial results demonstrate fundamental differences in the biota and biogeochemistry of the two aquifer complexes that trace back to the land uses in their respective recharge areas. They also show the importance of antecedent conditions on the impact of precipitation events on responses in terms of groundwater dynamics, chemistry and ecology. Thus we find signals of surface land use and events can be detected in the

  7. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  8. On the methane paradox: Transport from shallow water zones rather than in situ methanogenesis is the major source of CH4 in the open surface water of lakes

    Science.gov (United States)

    Encinas Fernández, Jorge; Peeters, Frank; Hofmann, Hilmar

    2016-10-01

    Estimates of global methane (CH4) emissions from lakes and the contributions of different pathways are currently under debate. In situ methanogenesis linked to algae growth was recently suggested to be the major source of CH4 fluxes from aquatic systems. However, based on our very large data set on CH4 distributions within lakes, we demonstrate here that methane-enriched water from shallow water zones is the most likely source of the basin-wide mean CH4 concentrations in the surface water of lakes. Consistently, the mean surface CH4 concentrations are significantly correlated with the ratio between the surface area of the shallow water zone and the entire lake, fA,s/t, but not with the total surface area. The categorization of CH4 fluxes according to fA,s/t may therefore improve global estimates of CH4 emissions from lakes. Furthermore, CH4 concentrations increase substantially with water temperature, indicating that seasonally resolved data are required to accurately estimate annual CH4 emissions.

  9. Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O((3)P) + Ethylene Reaction at High Collision Energy.

    Science.gov (United States)

    Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio; Fu, Bina; Bowman, Joel M

    2015-12-17

    The combustion relevant O((3)P) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs), which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy Ec of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135°. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by synergic full-dimensional quasiclassical trajectory surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical study extends and complements our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to vinoxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, with a clear tendency of the

  10. User's Guide: Database of literature pertaining to the unsaturated zone and surface water-ground water interactions at the Idaho National Engineering Laboratory

    International Nuclear Information System (INIS)

    Hall, L.F.

    1993-05-01

    Since its beginnings in 1949, hydrogeologic investigations at the Idaho National Engineering Laboratory (INEL) have resulted in an extensive collection of technical publications providing information concerning ground water hydraulics and contaminant transport within the unsaturated zone. Funding has been provided by the Department of Energy through the Department of Energy Idaho Field Office in a grant to compile an INEL-wide summary of unsaturated zone studies based on a literature search. University of Idaho researchers are conducting a review of technical documents produced at or pertaining to the INEL, which present or discuss processes in the unsaturated zone and surface water-ground water interactions. Results of this review are being compiled as an electronic database. Fields are available in this database for document title and associated identification number, author, source, abstract, and summary of information (including types of data and parameters). AskSam reg-sign, a text-based database system, was chosen. WordPerfect 5.1 copyright is being used as a text-editor to input data records into askSam

  11. Mapping porosity of the deep critical zone in 3D using near-surface geophysics, rock physics modeling, and drilling

    Science.gov (United States)

    Flinchum, B. A.; Holbrook, W. S.; Grana, D.; Parsekian, A.; Carr, B.; Jiao, J.

    2017-12-01

    Porosity is generated by chemical, physical and biological processes that work to transform bedrock into soil. The resulting porosity structure can provide specifics about these processes and can improve understanding groundwater storage in the deep critical zone. Near-surface geophysical methods, when combined with rock physics and drilling, can be a tool used to map porosity over large spatial scales. In this study, we estimate porosity in three-dimensions (3D) across a 58 Ha granite catchment. Observations focus on seismic refraction, downhole nuclear magnetic resonance logs, downhole sonic logs, and samples of core acquired by push coring. We use a novel petrophysical approach integrating two rock physics models, a porous medium for the saprolite and a differential effective medium for the fractured rock, that drive a Bayesian inversion to calculate porosity from seismic velocities. The inverted geophysical porosities are within about 0.05 m3/m3 of lab measured values. We extrapolate the porosity estimates below seismic refraction lines to a 3D volume using ordinary kriging to map the distribution of porosity in 3D up to depths of 80 m. This study provides a unique map of porosity on scale never-before-seen in critical zone science. Estimating porosity on these large spatial scales opens the door for improving and understanding the processes that shape the deep critical zone.

  12. 21 CFR 866.2850 - Automated zone reader.

    Science.gov (United States)

    2010-04-01

    ...) MEDICAL DEVICES IMMUNOLOGY AND MICROBIOLOGY DEVICES Microbiology Devices § 866.2850 Automated zone reader... surface of certain culture media used in disc-agar diffusion antimicrobial susceptibility tests. The...

  13. Oxygenated gasoline release in the unsaturated zone - Part 1: Source zone behavior.

    Science.gov (United States)

    Freitas, Juliana G; Barker, James F

    2011-11-01

    Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Surface-ionization field mass-spectrometry studies of nonequilibrium surface ionization

    International Nuclear Information System (INIS)

    Blashenkov, Nikolai M; Lavrent'ev, Gennadii Ya

    2007-01-01

    The ionization of polyatomic molecules on tungsten and tungsten oxide surfaces is considered for quasiequilibrium or essentially nonequilibrium conditions (in the latter case, the term nonequilibrium surface ionization is used for adsorbate ionization). Heterogeneous reactions are supposed to proceed through monomolecular decay of polyatomic molecules or fragments of multimolecular complexes. The nonequilibrium nature of these reactions is established. The dependences of the current density of disordered ions on the surface temperature, electric field strength, and ionized particle energy distribution are obtained in analytical form. Heterogeneous dissociation energies, the ionization potentials of radicals, and the magnitude of reaction departure from equilibrium are determined from experimental data, as are energy exchange times between reaction products and surfaces, the number of molecules in molecular complexes, and the number of effective degrees of freedom in molecules and complexes. In collecting the data a new technique relying on surface-ionization field mass-spectrometry was applied. (instruments and methods of investigation)

  15. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  16. Buried and Surface Polymetallic Nodule Distribution in the Eastern CLARION-CLIPPERTON Zone: Main Distinctions and Similarities

    Science.gov (United States)

    Kotlinski, R.; Stoyanova, V.

    The distribution pattern, abundance variations, morphology, chemical and mineralogical composition of buried polymetallic nodules in the eastern Clarion-Clipperton Zone (CCZ) are presented. Our observations are based on data collected from 59 boxcore stations, which comprise about 22.6% of all sampled stations in the Interoceanmetal exploration area site B2 in the eastern CCZ, with recorded buried and surface polymetallic nodules. The majority of stations with buried nodules (>90%) is below 4300 m water depth and is associated mainly with seafloor hills and slopes of ridges and depressions. Buried nodules lie completely beneath the active sediment-water boundary layer (with thickness range from 0 to 15 cm), and they are vertically recorded down to the 45 cm in sediment cores. Abundance of buried nodules varies from 0.2 to 22.1 kg/m2, averaging 3.2 kg/m2. By comparison, surface nodules are more abundant, varying from 0 to 20.2 kg/m2, averaging 10.3 kg/m2. As a general rule the size of buried nodules is larger than surface nodules, and >27% of recovered buried nodules exceed 10 cm in diameter. It is assumed that more than 90% of analyzed buried nodules have a diagenetic origin; however, the identification of factors and conditions responsible for their formation still remains unknown.

  17. Pulsed laser-assisted focused electron-beam-induced etching of titanium with XeF2: enhanced reaction rate and precursor transport.

    Science.gov (United States)

    Noh, J H; Fowlkes, J D; Timilsina, R; Stanford, M G; Lewis, B B; Rack, P D

    2015-02-25

    In order to enhance the etch rate of electron-beam-induced etching, we introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. The evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. The increased etch rate is attributed to photothermally enhanced Ti-F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

  18. The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

    Science.gov (United States)

    Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

    2018-03-01

    The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies

  19. Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

    Science.gov (United States)

    Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

    2016-03-29

    Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

  20. Hoof accelerations and ground reaction forces of Thoroughbred racehorses measured on dirt, synthetic, and turf track surfaces.

    Science.gov (United States)

    Setterbo, Jacob J; Garcia, Tanya C; Campbell, Ian P; Reese, Jennifer L; Morgan, Jessica M; Kim, Sun Y; Hubbard, Mont; Stover, Susan M

    2009-10-01

    To compare hoof acceleration and ground reaction force (GRF) data among dirt, synthetic, and turf surfaces in Thoroughbred racehorses. 3 healthy Thoroughbred racehorses. Forelimb hoof accelerations and GRFs were measured with an accelerometer and a dynamometric horseshoe during trot and canter on dirt, synthetic, and turf track surfaces at a racecourse. Maxima, minima, temporal components, and a measure of vibration were extracted from the data. Acceleration and GRF variables were compared statistically among surfaces. The synthetic surface often had the lowest peak accelerations, mean vibration, and peak GRFs. Peak acceleration during hoof landing was significantly smaller for the synthetic surface (mean + or - SE, 28.5g + or - 2.9g) than for the turf surface (42.9g + or - 3.8g). Hoof vibrations during hoof landing for the synthetic surface were dirt and turf surfaces. Peak GRF for the synthetic surface (11.5 + or - 0.4 N/kg) was 83% and 71% of those for the dirt (13.8 + or - 0.3 N/kg) and turf surfaces (16.1 + or - 0.7 N/kg), respectively. The relatively low hoof accelerations, vibrations, and peak GRFs associated with the synthetic surface evaluated in the present study indicated that synthetic surfaces have potential for injury reduction in Thoroughbred racehorses. However, because of the unique material properties and different nature of individual dirt, synthetic, and turf racetrack surfaces, extending the results of this study to encompass all track surfaces should be done with caution.

  1. Implementation of Solute Transport in the Vadose Zone into the `HYDRUS Package for MODFLOW'

    Science.gov (United States)

    Simunek, J.; Beegum, S.; Szymkiewicz, A.; Sudheer, K. P.

    2017-12-01

    The 'HYDRUS package for MODFLOW' was developed by Seo et al. (2007) and Twarakavi et al. (2008) to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package, which is based on the HYDRUS-1D model (Šimůnek et al., 2016) simulating unsaturated water flow in the vadose zone, was incorporated into MODFLOW (Harbaugh et al., 2000) simulating saturated groundwater flow. The HYDRUS package in the coupled model can be used to represent the effects of various unsaturated zone processes, including infiltration, evaporation, root water uptake, capillary rise, and recharge in homogeneous or layered soil profiles. The coupled model is effective in addressing spatially-variable saturated-unsaturated hydrological processes at the regional scale, allowing for complex layering in the unsaturated zone, spatially and temporarily variable water fluxes at the soil surface and in the root zone, and with alternating recharge and discharge fluxes (Twarakavi et al., 2008). One of the major limitations of the coupled model was that it could not be used to simulate at the same time solute transport. However, solute transport is highly dependent on water table fluctuations due to temporal and spatial variations in groundwater recharge. This is an important concern when the coupled model is used for analyzing groundwater contamination due to transport through the unsaturated zone. The objective of this study is to integrate the solute transport model (the solute transport part of HYDRUS-1D for the unsaturated zone and MT3DMS (Zheng and Wang, 1999; Zheng, 2009) for the saturated zone) into an existing coupled water flow model. The unsaturated zone component of the coupled model can consider solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption (Šimůnek and van Genuchten, 2008

  2. Surface science and catalysis

    International Nuclear Information System (INIS)

    Somorjai, G.A.

    1985-02-01

    Modern surface science studies have explored a large number of metal catalyst systems. Three classes of catalytic reactions can be identified: (1) those that occur over the metal surface; (2) reactions that take place on top of a strongly adsorbed overlayer and (3) reactions that occur on co-adsorbate modified surfaces. Case histories for each class are presented. 44 refs., 13 figs., 3 tabs

  3. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...... for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration...

  4. What happens when iron becomes wet? Observation of reactions at interfaces between liquid and metal surfaces

    CERN Document Server

    Kimura, M

    2003-01-01

    Synchrotron-radiation has been applied to investigation of interfaces between liquid and metal surfaces, with a special attention to corrosion. Three topics are shown: (1) nano structures of rusts formed on steel after atmospheric corrosion. Evolution of 'Fe(O, OH) sub 6 network' is the key to understand how the durable rusts prevent from formation of more rusts. (2) In situ observation of reactions at the interface has been carried out for localized corrosion of stainless steel. It is shown that change in states of Cr sup 3 sup + and Br sup - ions near the interface is deeply related with a breakout of the passivation film. (3) A structural phase transformation on a Cu sub 3 Au(001) surface was investigated. Ordering remains even at a temperature higher than the bulk-critical temperature, showing surface-induced ordering. These approaches gives us crucial information for a new steel-product. (author)

  5. Progress Report on the US Critical Zone Observatory Program

    Science.gov (United States)

    Barrera, E. C.

    2014-12-01

    The Critical Zone Observatory (CZO) program supported by the National Science Foundation originated from the recommendation of the Earth Science community published in the National Research Council report "Basic Research Opportunities in Earth Sciences" (2001) to establish natural laboratories to study processes and systems of the Critical Zone - the surface and near-surface environment sustaining nearly all terrestrial life. After a number of critical zone community workshops to develop a science plan, the CZO program was initiated in 2007 with three sites and has now grown to 10 sites and a National Office, which coordinates research, education and outreach activities of the network. Several of the CZO sites are collocated with sites supported by the US Long Term Ecological Research (LTER) and the Long Term Agricultural Research (LTAR) programs, and the National Ecological Observatory Network (NEON). Future collaboration with additional sites of these networks will add to the potential to answer questions in a more comprehensive manner and in a larger regional scale about the critical zone form and function. At the international level, CZOs have been established in many countries and strong collaborations with the US program have been in place for many years. The next step is the development of a coordinated international program of critical zone research. The success of the CZO network of sites can be measured in transformative results that elucidate properties and processes controlling the critical zone and how the critical zone structure, stores and fluxes respond to climate and land use change. This understanding of the critical zone can be used to enhance resilience and sustainability, and restore ecosystem function. Thus, CZO science can address major societal challenges. The US CZO network is a facility open to research of the critical zone community at large. Scientific data and information about the US program are available at www.criticalzone.org.

  6. Numerical exploration of a non-Newtonian Carreau fluid flow driven by catalytic surface reactions on an upper horizontal surface of a paraboloid of revolution, buoyancy and stretching at the free stream

    Directory of Open Access Journals (Sweden)

    I.L. Animasaun

    2017-12-01

    Full Text Available Geometrically, the upper pointed surface of an aircraft and bonnet of a car are examples of upper horizontal surfaces of a paraboloid of revolution (uhspr. The motion of these objects strongly depends on the boundary layer that is formed within the immediate space on it. However, each of these surfaces is neither a horizontal/vertical nor cone/wedge and neither a cone nor a wedge. This article presents the motion of 2-dimensional Blasius flow of Carreau fluid on the surface of such object. The case in which the reaction between the Carreau fluid and catalyst at the surface produces significant temperature differences which consequently set up buoyancy-driven flows within the boundary layer is investigated. Single first-order Arrhenius kinetics is adopted to model the reaction on the surface of the catalyst situated on uhspr which initiates the free convection. Suitable similarity variables are applied to non-dimensionalized, parameterized and reduce the governing partial differential equations to a coupled ordinary differential equations (BVP. The BVP is solved numerically using the shooting technique. Temperature distribution in the flow of viscoelastic Carreau fluid is greater than that of a Newtonian fluid. Local heat transfer rate decreases faster when the Carreau fluid is characterized as shear-thinning. Maximum concentration is guaranteed at a small value of power-law index n and large value of thickness parameter. Keywords: Viscoelastic-Carreau fluid, Catalitic surface, Paraboloid of revolution, Numerical method, Uhspr, Boundary layer analysis

  7. Coniferons forests in the thirty kilometer zone of the Chernobyl' NPP

    International Nuclear Information System (INIS)

    Kozubov, G.M.; Taskaev, A.I.; Zhdanova, N.V.; Kozlov, V.A.; Patov, A.I.; Galkina, E.V.; Kuziv, E.A.

    1992-01-01

    Four zones of pine forests are distinguished on basis of contamination degree: the lethal zone with complete pine ruin, 'red forest', the sublethal zone with partial pine daying off and mass branch dry up; zone of an average lesion with depression of growth processes and a morphose formation; zone of a weak exposure, where the radiation effect expressed in pine reproductive, sphere changes. It is noted, that the pine reproductive structures have most sensitivity, to the radiation induced ionization. Morphofunctional peculiaryties of the pine reaction to the radiation exposure in the accident region. A hypothesis in proposed. In accordance with the hypothesis the high radiosensitivity phenomenon of conifers is due to their two structural-metabolic peculiarities: by a considerable dimensions of nuclei-chromosomal complex at the high nucleoproteides content and by a lipid metabolism predomination in the all important links of the metabolism. 24 refs.; 3 tabs

  8. Realization of the Zone Length Measurement during Zone Refining Process via Implementation of an Infrared Camera

    Directory of Open Access Journals (Sweden)

    Danilo C. Curtolo

    2018-05-01

    Full Text Available Zone refining, as the currently most common industrial process to attain ultrapure metals, is influenced by a variety of factors. One of these parameters, the so-called “zone length”, affects not only the ultimate concentration distribution of impurities, but also the rate at which this distribution is approached. This important parameter has however neither been investigated experimentally, nor ever varied for the purpose of optimization. This lack of detections may be due to the difficult temperature measurement of a moving molten area in a vacuum system, of which the zone refining methodology is comprised. Up to now, numerical simulation as a combination of complex mathematical calculations, as well as many assumptions has been the only way to reveal it. This paper aims to propose an experimental method to accurately measure the molten zone length and to extract helpful information on the thermal gradient, temperature profile and real growth rate in the zone refining of an exemplary metal, in this case aluminum. This thermographic method is based on the measurement of the molten surface temperature via an infrared camera, as well as further data analysis through the mathematical software MATLAB. The obtained results show great correlation with the visual observations of zone length and provide helpful information to determine the thermal gradient and real growth rate during the whole process. The investigations in this paper approved the application of an infrared camera for this purpose as a promising technique to automatically control the zone length during a zone refining process.

  9. The Habitable Zone and Extreme Planetary Orbits

    OpenAIRE

    Kane, Stephen R.; Gelino, Dawn M.

    2012-01-01

    The habitable zone for a given star describes the range of circumstellar distances from the star within which a planet could have liquid water on its surface, which depends upon the stellar properties. Here we describe the development of the habitable zone concept, its application to our own solar system, and its subsequent application to exoplanetary systems. We further apply this to planets in extreme eccentric orbits and show how they may still retain life-bearing properties depending upon...

  10. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2016-02-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012) tailored for sea-ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on surface roughness is recognised, and

  11. Observations of surface momentum exchange over the marginal-ice-zone and recommendations for its parameterization

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2015-10-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parameterization of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parameterization scheme (Lüpkes et al., 2012) tailored for sea ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parameterization schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement is found to hold for subsets of the data from different locations despite differences in sea ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea ice morphology and floe size on surface roughness is

  12. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  13. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    2008-07-01

    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  14. Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

    Science.gov (United States)

    Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

    2018-05-29

    Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

  15. Temperature dependence on sodium-water chemical reaction

    International Nuclear Information System (INIS)

    Tamura, Kenta; Deguchi, Yoshihiro; Suzuki, Koichi; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

    2012-01-01

    In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. A quasi one-dimensional flame model is also applied to a sodium-water counter-flow reaction field. Temperature, H 2 , H 2 O, OH, Na and Particulate matter were measured using laser induced fluorescence and CARS in the counter-flow reaction field. The temperature of the reaction field was also modified to reduce the condensation of Na in the reaction zone. (author)

  16. Library of Antifouling Surfaces Derived From Natural Amino Acids by Click Reaction.

    Science.gov (United States)

    Xu, Chen; Hu, Xin; Wang, Jie; Zhang, Ye-Min; Liu, Xiao-Jiu; Xie, Bin-Bin; Yao, Chen; Li, Yi; Li, Xin-Song

    2015-08-12

    Biofouling is of great concern in numerous applications ranging from ophthalmological implants to catheters, and from bioseparation to biosensors. In this report, a general and facile strategy to combat surface fouling is developed by grafting of amino acids onto polymer substrates to form zwitterionic structure through amino groups induced epoxy ring opening click reaction. First of all, a library of poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) hydrogels with zwitterionic surfaces were prepared, resulting in the formation of pairs of carboxyl anions and protonated secondary amino cations. The analysis of attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the successful immobilization of amino acids on the hydrogel surfaces. After that, the contact angle and equilibrium water content of the modified hydrogels showed that the hydrogels exhibited improved hydrophilicity compared with the parent hydrogel. Furthermore, the protein deposition was evaluated by bicinchoninic acid assay using bovine serum albumin (BSA) and lysozyme as models. The results indicated that the performance of the hydrogels was determined by the nature of incorporated amino acid: the hydrogels incorporated with neutral amino acids had nonspecific antiadsorption capability to both BSA and lysozyme; the hydrogels incorporated with charged amino acids showed antiadsorption behaviors against protein with same charge and enhanced adsorption to the protein with opposite charge; the optimal antiadsorption performance was observed on the hydrogels incorporated with polar amino acids with a hydroxyl residual. The improvement of antiprotein fouling of the neutral amino acids grafted hydrogels can be ascribed to the formation of zwitterionic surfaces. Finally, a couple of soft contact lenses grafted with amino acids were fabricated having improved antifouling property and hydrophilicity. The result demonstrated the success of

  17. Mass Spectral Investigation of Laboratory Made Tholins and Their Reaction Products: Implications to Tholin Surface Chemistry on Titan

    Science.gov (United States)

    Somogyi, Arpad; Smith, M. A.

    2006-09-01

    The success of the Huygens mission does not overshadow the importance of laboratory simulations of gas-phase and surface reactions that might occur in Titan's atmosphere and surface, respectively. We present here our latest results on chemical reactions (hydrolysis, peroxidation and hydrogenation) of laboratory made tholins obtained by FT-ICR mass spectrometry. The laboratory synthesis of tholins has been described in our earlier papers [1,2]. Overall, we conclude that our laboratory tholins are reactive materials that undergo fast hydrolysis, oxidation and reduction. Thus, if the tholin on Titan's surface resemble our laboratory made tholins, it can be considered as a potential starting material for several synthetic processes that can provide organic compounds of pre-biotic interest. Hydrolysis reactions occur with rate constants of 2-10 hour-1 at room temperature. Formal water addition to several species of CxHyNz has been observed by detecting the formation of CxHy+2NzO species. MS/MS fragmentation of the oxygen containing ions leads to the loss of water, ammonia, HCN, acetonitrile, etc. This suggests that tholin hydrolysis may occur in temporary melted ponds of water/ammonia ice on Titan. Peroxidation, which can be considered as a very harsh oxidation, leads to mono-, and multiple oxygenated compounds within a few minutes. The MS/MS fragmentation of these compounds suggests the presence of organic amides and, presumably, amino acid like compounds. Hydrogenation leads to compounds in which the originally present carbon-carbon or carbon-nitrogen double and triple bonds are saturated. H/D exchange experiments show different kinetics depending on the degree of unsaturation/saturation and the number of N atoms. [1] Sarker, N.; Somogyi, A.; Lunine, J. I.; Smith, M. A. Astrobiology, 2003, 3, 719-726. [2] Somogyi, A.; Oh, C-H.; Lunine, J. I.; Smith, M. A. J. Am. Soc. Mass Spectrom. 2005, 16, 850-859.

  18. Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

    Science.gov (United States)

    Abbas, N.; Madix, R. J.

    The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

  19. Reactions and Surface Transformations of a Bone-Bioactive Material in a Simulated Microgravity Environment

    Science.gov (United States)

    Radin, S.; Ducheyne, P.; Ayyaswamy, P. S.

    1999-01-01

    A comprehensive program to investigate the expeditious in vitro formation of three-dimensional bone-like tissue is currently underway at the University of Pennsylvania. The study reported here forms a part of that program. Three-dimensional bone-like tissue structures may be grown under the simulated microgravity conditions of NASA designed Rotating Wall Bioreactor Vessels (RWV's). Such tissue growth will have wide clinical applications. In addition, an understanding of the fundamental changes that occur to bone cells under simulated microgravity would yield important information that will help in preventing or minimizing astronaut bone loss, a major health issue with travel or stay in space over long periods of time. The growth of three-dimensional bone-like tissue structures in RWV's is facilitated by the use of microcarriers which provide structural support. If the microcarrier material additionally promotes bone cell growth, then it is particularly advantageous to employ such microcarriers. We have found that reactive, bone-bioactive glass (BBG) is an attractive candidate for use as microcarrier material. Specifically, it has been found that BBG containing Ca- and P- oxides upregulates osteoprogenitor cells to osteoblasts. This effect on cells is preceded by BBG reactions in solution which result in the formation of a Ca-P surface layer. This surface further transforms to a bone-like mineral (i.e., carbonated crystalline hydroxyapatite (c-HA)). At normal gravity, time-dependent, immersion-induced BBG reactions and transformations are greatly affected both by variations in the composition of the milieu in which the glass is immersed and on the immersion conditions. However, the nature of BBG reactions and phase transformations under the simulated microgravity conditions of RWV's are unknown, and must be understood in order to successfully use BBG as microcarrier material in RWV'S. In this paper, we report some of our recent findings in this regard using

  20. Propagation of hydroclimatic variability through the critical zone

    Science.gov (United States)

    Porporato, A. M.; Calabrese, S.; Parolari, A.

    2016-12-01

    The interaction between soil moisture dynamics and mineral-weathering reactions (e.g., ion exchange, precipitation-dissolution) affects the availability of nutrients to plants, composition of soils, soil acidification, as well as CO2 sequestration. Across the critical zone (CZ), this interaction is responsible for propagating hydroclimatic fluctuations to deeper soil layers, controlling weathering rates via leaching events which intermittently alter the alkalinity levels. In this contribution, we analyze these dynamics using a stochastic modeling approach based on spatially lumped description of soil hydrology and chemical weathering reactions forced by multi-scale temporal hydrologic variability. We quantify the role of soil moisture dynamics in filtering the rainfall fluctuations through its impacts on soil water chemistry, described by a system of ordinary differential equations (and algebraic equations, for the equilibrium reactions), driving the evolution of alkalinity, pH, the chemical species of the soil solution, and the mineral-weathering rate. A probabilistic description of the evolution of the critical zone is thus obtained, allowing us to describe the CZ response to long-term climate fluctuations, ecosystem and land-use conditions, in terms of key variables groups. The model is applied to the weathering rate of albite in the Calhoun CZ observatory and then extended to explore similarities and differences across other CZs. Typical time scales of response and degrees of sensitivities of CZ to hydroclimatic fluctuations and human forcing are also explored.

  1. Magnetic Fields in the Solar Convection Zone

    Directory of Open Access Journals (Sweden)

    Fan Yuhong

    2004-07-01

    Full Text Available Recent studies of the dynamic evolution of magnetic flux tubes in the solar convection zone are reviewed with focus on emerging flux tubes responsible for the formation of solar active regions. The current prevailing picture is that active regions on the solar surface originate from strong toroidal magnetic fields generated by the solar dynamo mechanism at the thin tachocline layer at the base of the solar convection zone. Thus the magnetic fields need to traverse the entire convection zone before they reach the photosphere to form the observed solar active regions. This review discusses results with regard to the following major topics: 1. the equilibrium properties of the toroidal magnetic fields stored in the stable overshoot region at the base of the convection zone, 2. the buoyancy instability associated with the toroidal magnetic fields and the formation of buoyant magnetic flux tubes, 3. the rise of emerging flux loops through the solar convective envelope as modeled by the thin flux tube calculations which infer that the field strength of the toroidal magnetic fields at the base of the solar convection zone is significantly higher than the value in equipartition with convection, 4. the minimum twist needed for maintaining cohesion of the rising flux tubes, 5. the rise of highly twisted kink unstable flux tubes as a possible origin of d -sunspots, 6. the evolution of buoyant magnetic flux tubes in 3D stratified convection, 7. turbulent pumping of magnetic flux by penetrative compressible convection, 8. an alternative mechanism for intensifying toroidal magnetic fields to significantly super-equipartition field strengths by conversion of the potential energy associated with the superadiabatic stratification of the solar convection zone, and finally 9. a brief overview of our current understanding of flux emergence at the surface and post-emergence evolution of the subsurface magnetic fields.

  2. Tc(VII) and Cr(VI) Interaction with Naturally Reduced Ferruginous Smectite from a Redox Transition Zone.

    Science.gov (United States)

    Qafoku, Odeta; Pearce, Carolyn I; Neumann, Anke; Kovarik, Libor; Zhu, Mengqiang; Ilton, Eugene S; Bowden, Mark E; Resch, Charles T; Arey, Bruce W; Arenholz, Elke; Felmy, Andrew R; Rosso, Kevin M

    2017-08-15

    Fe(II)-rich clay minerals found in subsurface redox transition zones (RTZs) can serve as important sources of electron equivalents limiting the transport of redox-active contaminants. While most laboratory reactivity studies are based on reduced model clays, the reactivity of naturally reduced field samples remains poorly explored. Characterization of the clay size fraction of a fine-grained unit from the RTZ interface at the Hanford site, Washington, including mineralogy, crystal chemistry, and Fe(II)/(III) content, indicates that ferruginous montmorillonite is the dominant mineralogical component. Oxic and anoxic fractions differ significantly in Fe(II) natural content, but Fe TOTAL remains constant, demonstrating no Fe loss during its reduction-oxidation cyclings. At native pH of 8.6, the anoxic fraction, despite its significant Fe(II), ∼23% of Fe TOTAL , exhibits minimal reactivity with TcO 4 - and CrO 4 2- and much slower reaction kinetics than those measured in studies with biologically/chemically reduced model clays. Reduction capacity is enhanced by added/sorbed Fe(II) (if Fe(II) SORBED > 8% clay Fe(II) LABILE ); however, the kinetics of this conceptually surface-mediated reaction remain sluggish. Surface-sensitive Fe L-edge X-ray absorption spectroscopy shows that Fe(II) SORBED and the resulting reducing equivalents are not available in the outermost few nanometers of clay surfaces. Slow kinetics thus appear related to diffusion-limited access to electron equivalents retained within the clay mineral structure.

  3. Excimer laser surface modification: Process and properties

    Energy Technology Data Exchange (ETDEWEB)

    Jervis, T.R.; Nastasi, M. [Los Alamos National Lab., NM (United States); Hirvonen, J.P. [Technical Research Institute, Espoo (Finland). Metallurgy Lab.

    1992-12-01

    Surface modification can improve materials for structural, tribological, and corrosion applications. Excimer laser light has been shown to provide a rapid means of modifying surfaces through heat treating, surface zone refining, and mixing. Laser pulses at modest power levels can easily melt the surfaces of many materials. Mixing within the molten layer or with the gas ambient may occur, if thermodynamically allowed, followed by rapid solidification. The high temperatures allow the system to overcome kinetic barriers found in some ion mixing experiments. Alternatively, surface zone refinement may result from repeated melting-solidification cycles. Ultraviolet laser light couples energy efficiently to the surface of metallic and ceramic materials. The nature of the modification that follows depends on the properties of the surface and substrate materials. Alloying from both gas and predeposited layer sources has been observed in metals, semiconductors, and ceramics as has surface enrichment of Cr by zone refinement of stainless steel. Rapid solidification after melting often results in the formation of nonequilibrium phases, including amorphous materials. Improved surface properties, including tribology and corrosion resistance, are observed in these materials.

  4. Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

    Science.gov (United States)

    Assiongbon, K. A.; Roy, D.

    2005-12-01

    Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

  5. Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

    Science.gov (United States)

    Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

    2018-04-12

    Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

  6. State-of-stress in magmatic rift zones: Predicting the role of surface and subsurface topography

    Science.gov (United States)

    Oliva, S. J. C.; Ebinger, C.; Rivalta, E.; Williams, C. A.

    2017-12-01

    Continental rift zones are segmented along their length by large fault systems that form in response to extensional stresses. Volcanoes and crustal magma chambers cause fundamental changes to the density structure, load the plates, and alter the state-of-stress within the crust, which then dictates fracture orientation. In this study, we develop geodynamic models scaled to a structure, petrologic and thermodynamic studies constrain material densities, and seismicity and structural analyses constrain active and time-averaged kinematics. This area is an ideal test area because a 60º stress rotation is observed in time-averaged fault and magma intrusion, and in local seismicity, and because this was the site of a large volume dike intrusion and seismic sequence in 2007. We use physics-based 2D and 3D models (analytical and finite elements) constrained by data from active rift zones to quantify the effects of loading on state-of-stress. By modeling varying geometric arrangements, and density contrasts of topographic and subsurface loads, and with reasonable regional extensional forces, the resulting state-of-stress reveals the favored orientation for new intrusions. Although our models are generalized, they allow us to evaluate whether a magmatic system (surface and subsurface) can explain the observed stress rotation, and enable new intrusions, new faults, or fault reactivation with orientations oblique to the main border faults. Our results will improve our understanding of the different factors at play in these extensional regimes, as well as contribute to a better assessment of the hazards in the area.

  7. Similarity and Difference between the South Atlantic Convergence Zone and the Baiu Frontal Zone Simulated by an AGCM

    OpenAIRE

    Kozo, NINOMIYA; Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology

    2007-01-01

    Features of the South Atlantic convergence zone (SACZ) and the Baiu frontal zone (BFZ) simulated by an AGCM (T106L56: a primitive equation spectral model which has 56 σ-levels and triangular spectral truncation at wave-number 106) are studied. The 24-year integration, from 1979 to 2002, by the model constrained by observed sea-surface temperature and sea-ice distribution, is used for this study. The detailed analysis is made for the typical case of SACZ and BFZ selected from data in 1985-1996...

  8. Reaction of Tri-methylaluminum on Si (001) Surface for Initial Aluminum Oxide Thin-Film Growth

    International Nuclear Information System (INIS)

    Kim, Dae Hee; Kim, Dae Hyun; Jeong, Yong Chan; Seo, Hwa Il; Kim, Yeong Cheol

    2010-01-01

    We studied the reaction of tri-methylaluminum (TMA) on hydroxyl (OH)-terminated Si (001) surfaces for the initial growth of aluminum oxide thin-films using density functional theory. TMA was adsorbed on the oxygen atom of OH due to the oxygen atom's lone pair electrons. The adsorbed TMA reacted with the hydrogen atom of OH to produce a di-methylaluminum group (DMA) and methane with an energy barrier of 0.50 eV. Low energy barriers in the range of 0 - 0.11 eV were required for DMA migration to the inter-dimer, intra-dimer, and inter-row sites on the surface. A unimethylaluminum group (UMA) was generated at each site with low energy barriers in the range of 0.21 - 0.25 eV. Among the three sites, the inter-dimer site was the most probable for UMA formation

  9. Delineation of marine ecosystem zones in the northern Arabian Sea during winter

    Directory of Open Access Journals (Sweden)

    S. Shalin

    2018-03-01

    Full Text Available The spatial and temporal variability of marine autotrophic abundance, expressed as chlorophyll concentration, is monitored from space and used to delineate the surface signature of marine ecosystem zones with distinct optical characteristics. An objective zoning method is presented and applied to satellite-derived Chlorophyll a (Chl a data from the northern Arabian Sea (50–75° E and 15–30° N during the winter months (November–March. Principal component analysis (PCA and cluster analysis (CA were used to statistically delineate the Chl a into zones with similar surface distribution patterns and temporal variability. The PCA identifies principal components of variability and the CA splits these into zones based on similar characteristics. Based on the temporal variability of the Chl a pattern within the study area, the statistical clustering revealed six distinct ecological zones. The obtained zones are related to the Longhurst provinces to evaluate how these compared to established ecological provinces. The Chl a variability within each zone was then compared with the variability of oceanic and atmospheric properties viz. mixed-layer depth (MLD, wind speed, sea-surface temperature (SST, photosynthetically active radiation (PAR, nitrate and dust optical thickness (DOT as an indication of atmospheric input of iron to the ocean. The analysis showed that in all zones, peak values of Chl a coincided with low SST and deep MLD. The rate of decrease in SST and the deepening of MLD are observed to trigger the algae bloom events in the first four zones. Lagged cross-correlation analysis shows that peak Chl a follows peak MLD and SST minima. The MLD time lag is shorter than the SST lag by 8 days, indicating that the cool surface conditions might have enhanced mixing, leading to increased primary production in the study area. An analysis of monthly climatological nitrate values showed increased concentrations associated with the deepening

  10. Delineation of marine ecosystem zones in the northern Arabian Sea during winter

    Science.gov (United States)

    Shalin, Saleem; Samuelsen, Annette; Korosov, Anton; Menon, Nandini; Backeberg, Björn C.; Pettersson, Lasse H.

    2018-03-01

    The spatial and temporal variability of marine autotrophic abundance, expressed as chlorophyll concentration, is monitored from space and used to delineate the surface signature of marine ecosystem zones with distinct optical characteristics. An objective zoning method is presented and applied to satellite-derived Chlorophyll a (Chl a) data from the northern Arabian Sea (50-75° E and 15-30° N) during the winter months (November-March). Principal component analysis (PCA) and cluster analysis (CA) were used to statistically delineate the Chl a into zones with similar surface distribution patterns and temporal variability. The PCA identifies principal components of variability and the CA splits these into zones based on similar characteristics. Based on the temporal variability of the Chl a pattern within the study area, the statistical clustering revealed six distinct ecological zones. The obtained zones are related to the Longhurst provinces to evaluate how these compared to established ecological provinces. The Chl a variability within each zone was then compared with the variability of oceanic and atmospheric properties viz. mixed-layer depth (MLD), wind speed, sea-surface temperature (SST), photosynthetically active radiation (PAR), nitrate and dust optical thickness (DOT) as an indication of atmospheric input of iron to the ocean. The analysis showed that in all zones, peak values of Chl a coincided with low SST and deep MLD. The rate of decrease in SST and the deepening of MLD are observed to trigger the algae bloom events in the first four zones. Lagged cross-correlation analysis shows that peak Chl a follows peak MLD and SST minima. The MLD time lag is shorter than the SST lag by 8 days, indicating that the cool surface conditions might have enhanced mixing, leading to increased primary production in the study area. An analysis of monthly climatological nitrate values showed increased concentrations associated with the deepening of the mixed layer. The

  11. Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

    Science.gov (United States)

    Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

    2007-01-01

    A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

  12. Effect of surface functionalisation on the interaction of iron oxide nanoparticles with polymerase chain reaction.

    Science.gov (United States)

    Aysan, Ayse Beyza; Knejzlík, Zdeněk; Ulbrich, Pavel; Šoltys, Marek; Zadražil, Aleš; Štěpánek, František

    2017-05-01

    The combination of nanoparticles with the polymerase chain reaction (PCR) can have benefits such as easier sample handling or higher sensitivity, but also drawbacks such as loss of colloidal stability or inhibition of the PCR. The present work systematically investigates the interaction of magnetic iron oxide nanoparticles (MIONs) with the PCR in terms of colloidal stability and potential PCR inhibition due to interaction between the PCR components and the nanoparticle surface. Several types of MIONs with and without surface functionalisation by sodium citrate, dextran and 3-aminopropyl-triethoxysilane (APTES) were prepared and characterised by Transmission Electron Microscopy (TEM), dynamic light scattering (DLS) and Fourier Transform Infrared (FT-IR) spectroscopy. Colloidal stability in the presence of the PCR components was investigated both at room temperature and under PCR thermo-cycling. Dextran-stabilized MIONs show the best colloidal stability in the PCR mix at both room and elevated temperatures. Citrate- and APTES-stabilised as well as uncoated MIONs show a comparable PCR inhibition near the concentration 0.1mgml -1 while the inhibition of dextran stabilized MIONs became apparent near 0.5mgml -1 . It was demonstrated that the PCR could be effectively carried out even in the presence of elevated concentration of MIONs up to 2mgml -1 by choosing the right coating approach and supplementing the reaction mix by critical components, Taq DNA polymerase and Mg 2+ ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Alteration zones: are they a good target for gold deposits in Egypt

    International Nuclear Information System (INIS)

    Botros, N.S.

    2002-01-01

    Extensive rock alterations are a clearly visible characteristic of most Egyptian gold deposits and occurrences. The alterations occur either surrounding the auriferous quartz veins and/or structurally controlled by specific structural features, such as fractures and shear surfaces. Some samples of these alteration zones have proved to be anomalously enriched in gold while others are completely barren. Accordingly there is a controversy on the merit of alteration zones as good lead to gold. Here, the various types of wall rocks wall-rock alteration are reviewed with a discussion on the possible reaction that could have generated them. It is concluded that two main styles of alterations could be recognized in the field. The first results during the liberation of gold from the source rocks, and is characterized by being widely distributed and spatial relation to major structures. The second style, however, is related to the deposition of gold and is recognizable only within a few meters of the auriferous quartz veins. The potentiality of each style is discussed and applications of concept are offered. In general, alterations accompanying the liberation of gold are not completely devoid of gold, but may still retain some gold depending on the mineralogical siting of gold in the source rocks. Moreover, this type of alteration is a good criterion for the presence of gold in the nearby sites. Alterations accompanying deposition of gold, on the other hand, constitute a good target for gold particularly the portions that are dissected by minor quartz veins, veinlets and stockworks (silicification) where gold is believed to migrate to such sites with silica liberated during the different types of alterations. The presence of some efficient precipitants, such as sulphides, carbonates, clay minerals, sericites, iron oxides, chlorite and graphite in the alteration zones is a good indicator of the alteration zone. (author)

  14. Heterogeneous hyporheic zone dechlorination of a TCE groundwater plume discharging to an urban river reach.

    Science.gov (United States)

    Freitas, Juliana G; Rivett, Michael O; Roche, Rachel S; Durrant Neé Cleverly, Megan; Walker, Caroline; Tellam, John H

    2015-02-01

    The typically elevated natural attenuation capacity of riverbed-hyporheic zones is expected to decrease chlorinated hydrocarbon (CHC) groundwater plume discharges to river receptors through dechlorination reactions. The aim of this study was to assess physico-chemical processes controlling field-scale variation in riverbed-hyporheic zone dechlorination of a TCE groundwater plume discharge to an urban river reach. The 50-m long pool-riffle-glide reach of the River Tame in Birmingham (UK) studied is a heterogeneous high energy river environment. The shallow riverbed was instrumented with a detailed network of multilevel samplers. Freeze coring revealed a geologically heterogeneous and poorly sorted riverbed. A chlorine number reduction approach provided a quantitative indicator of CHC dechlorination. Three sub-reaches of contrasting behaviour were identified. Greatest dechlorination occurred in the riffle sub-reach that was characterised by hyporheic zone flows, moderate sulphate concentrations and pH, anaerobic conditions, low iron, but elevated manganese concentrations with evidence of sulphate reduction. Transient hyporheic zone flows allowing input to varying riverbed depths of organic matter are anticipated to be a key control. The glide sub-reach displayed negligible dechlorination attributed to the predominant groundwater baseflow discharge condition, absence of hyporheic zone, transition to more oxic conditions and elevated sulphate concentrations expected to locally inhibit dechlorination. The tail-of-pool-riffle sub-reach exhibited patchy dechlorination that was attributed to sub-reach complexities including significant flow bypass of a low permeability, high organic matter, silty unit of high dechlorination potential. A process-based conceptual model of reach-scale dechlorination variability was developed. Key findings of practitioner relevance were: riverbed-hyporheic zone CHC dechlorination may provide only a partial, somewhat patchy barrier to CHC

  15. Studies in the reaction dynamics of beam-gas chemiluminescent reactions

    International Nuclear Information System (INIS)

    Prisant, M.G.

    1984-01-01

    This thesis develops techniques for the analysis and interpretation of data obtained from beam-gas chemiluminescence experiments. These techniques are applied to experimental studies of atom transfer reactions of the type A + BC → AB + C. A procedure is developed for determining the product rotational alignment in the center-of-mass frame from polarization measurements of chemiluminescent atom-diatom exchange reactions under beam-gas conditions. Knowledge of a vector property of a reaction, such as product alignment, provides information on the disposition of angular momentum by a chemical reaction. Fluorescence polarization and hence product alignment are measured for two prototype reactions. The reaction of metastable calcium atoms with hydrogen-chloride gas yields highly aligned calcium-chloride product which exhibits little variation of alignment with vibrational state. The reaction of ground-state calcium with fluorine gas yields moderately aligned product which shows strong variation of alignment with vibration. A multi-surface direct-interaction model is developed to interpret product alignment and population data. The predictions of this model for the reaction of calcium with fluorine show reasonable agreement with experiment

  16. Distribution of 210Pb activity concentrations in marine surface sediments within East Coast Peninsula Malaysia Exclusive Economic Zone (EEZ)

    International Nuclear Information System (INIS)

    Ahmad Sanadi Abu Bakar; Zaharudin Ahmad

    2010-01-01

    A sampling expedition into the East Coast Peninsula Malaysia Exclusive Economic Zone (EEZ) was carried in June 2008. Marine surface sediment samples were taken and the activity concentrations of 210 Pb have been determined. Its distribution was plotted and the findings show that the activity concentrations decline from north to south. On the other hand, the activity concentrations are increasing from west to east right to the edge of the EEZ. The highest activity concentrations were found to be near offshore oil platforms. The 210 Pb activity concentrations were found to be in the range of 18.3 - 123.1 Bq/ kg. (author)

  17. Adsorption of cadmium ions on nickel surface skeleton catalysts and its effect on reaction of cathodic hydrogen evolution

    International Nuclear Information System (INIS)

    Korovin, N.V.; Udris, E.Ya.; Savel'eva, O.N.

    1986-01-01

    Cadmium adsorption from different concentration CdSO 4 solutions on nickel surface skeleton catalysts (Ni ssc ) is studied by recording of polarization and potentiodynamic curves using electron microscopy and X-ray spectrometry. Main regularities of cadmium adsorption on Ni ssc are shown to be similar to those on smooth and skeleton nickel. A conclusion is drawn that increase of catalytic activity in reaction of cathodic hydrogen evolution from alkali solutions of Ni ssc base electrodes after their treatment in solutions containing Cd 2+ ions is due to irreversible desorption of strongly and averagely bound hydrogen from electrode surface at cadmium adsorption on them

  18. Vadose Zone Fate and Transport Simulation of Chemicals Associated with Coal Seam Gas Extraction

    Science.gov (United States)

    Simunek, J.; Mallants, D.; Jacques, D.; Van Genuchten, M.

    2017-12-01

    The HYDRUS-1D and HYDRUS (2D/3D) computer software packages are widely used finite element models for simulating the one-, and two- or three-dimensional movement of water, heat, and multiple solutes in variably-saturated media, respectively. While the standard HYDRUS models consider only the fate and transport of individual solutes or solutes subject to first-order degradation reactions, several specialized HYDRUS add-on modules can simulate far more complex biogeochemical processes. The objective of this presentation is to provide an overview of the HYDRUS models and their add-on modules, and to demonstrate applications of the software to the subsurface fate and transport of chemicals involved in coal seam gas extraction and water management operations. One application uses the standard HYDRUS model to evaluate the natural soil attenuation potential of hydraulic fracturing chemicals and their transformation products in case of an accidental release. By coupling the processes of retardation, first-order degradation and convective-dispersive transport of the biocide bronopol and its degradation products, we demonstrated how natural attenuation reduces initial concentrations by more than a factor of hundred in the top 5 cm of the vadose zone. A second application uses the UnsatChem module to explore the possible use of coal seam gas produced water for sustainable irrigation. Simulations with different irrigation waters (untreated, amended with surface water, and reverse osmosis treated) provided detailed results regarding chemical indicators of soil and plant health, notably SAR, EC and sodium concentrations. A third application uses the coupled HYDRUS-PHREEQC module to analyze trace metal transport involving cation exchange and surface complexation sorption reactions in the vadose zone leached with coal seam gas produced water following some accidental water release scenario. Results show that the main process responsible for trace metal migration is complexation of

  19. Reaction-diffusion fronts with inhomogeneous initial conditions

    Energy Technology Data Exchange (ETDEWEB)

    Bena, I [Departement de Physique Theorique, Universite de Geneve, CH-1211 Geneva 4 (Switzerland); Droz, M [Departement de Physique Theorique, Universite de Geneve, CH-1211 Geneva 4 (Switzerland); Martens, K [Departement de Physique Theorique, Universite de Geneve, CH-1211 Geneva 4 (Switzerland); Racz, Z [Institute for Theoretical Physics, Eoetvoes University, 1117 Budapest (Hungary)

    2007-02-14

    Properties of reaction zones resulting from A+B {yields} C type reaction-diffusion processes are investigated by analytical and numerical methods. The reagents A and B are separated initially and, in addition, there is an initial macroscopic inhomogeneity in the distribution of the B species. For simple two-dimensional geometries, exact analytical results are presented for the time evolution of the geometric shape of the front. We also show using cellular automata simulations that the fluctuations can be neglected both in the shape and in the width of the front.

  20. Surface analytical investigations of the thermal behaviour of passivated Zircaloy-4 surfaces and of the reaction behaviour of iodine with Zircaloy-4 surfaces

    International Nuclear Information System (INIS)

    Kaufmann, R.

    1988-07-01

    In the first part of the present work the thermal behaviour of atmospherically oxidized Zircaloy-4 samples was investigated at various temperatures. In a next step the amount of iodine adsorbed at the metallic surface was determined as well at room temperature with varying iodine exposures as for constant exposure but varying temperatures. Furthermore, the zirconium iodide species resulting from the interaction of iodine with the Zircaloy-4 and desorbed at higher temperatures were identified by means of residual gas analysis. During these studies it was found that the oxidic overlayer of the passivated Zircaloy-4 samples is decomposed at temperatures above 200 0 C. The iodine uptake at metallic surfaces (cleaned by Ar-ion sputtering) at room temperature slows markedly down after formation of a closed zirconium-iodide overlayer and consequently the further reaction proceeds diffusion-controlled. At 200 0 C ZrI 4 is formed being the thermodynamically most stable Zr-iodide. During desorption experiments using iodine exposed Zircaloy-4 samples the release of ZrI 4 was proved. The results obtained from the various experiments are finally discussed with respect to the iodine-induced stress corrosion cracking process and the underlying basic mechanisms and a transport mechanism for the SCC in nuclear fuel rods is proposed. (orig./RB) [de

  1. Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

  2. Light-induced heterogeneous reactions of NO2 on indoor surfaces: How they affect the balance of nitrous acid

    Science.gov (United States)

    Gomez Alvarez, E.; Soergel, M.; Bassil, S.; Zetzsch, C.; Gligorovski, S.; Wortham, H.

    2011-12-01

    Nitrous acid (HONO) is an important indoor pollutant. The adverse health effects due to the formation of nitrosamines are well known. HONO acts as a nitrosating agent after wall reactions of HONO with nicotine [Sleiman et al., 2010]. Indoor air can be surprisingly rich in HONO (homes with fireplaces, stoves, gas heating and cooking) and also surfaces are abundant. High HONO concentrations have been measured in indoor environments, from the direct emissions and heterogeneous reactions of NO2 in darkness. However, the measured HONO concentrations do not correspond to the HONO levels determined by the models [Carslaw, 2007]. We have tested in a flow tube reactor on-line coupled to a NOx analyzer and a sensitive Long Path Absorption Photometry instrument, the behaviour of various indoor surfaces towards NO2 under simulated solar light irradiation (λ= 300-700 nm). Our study has allowed us to obtain a deeper knowledge on the mechanisms of heterogeneous formation of HONO, quantifying the dependence of HONO formation on behalf of NO2 concentration and relative humidity and the enhancement of HONO formation in the presence of light. Pyrex, acidic detergent, alkaline detergent, paint and lacquer were tested on behalf of their heterogeneous reactivity towards NO2 in the absence and in presence of light. The results obtained demonstrated that indoor surfaces are photo-chemically active under atmospherically relevant conditions. The strongly alkaline surfaces (such as certain types of detergent) show a strong long-term uptake capacity. However, other surfaces such as detergents with a more acidic character released HONO. In some cases such as paint and varnish, a strong HONO release with light was detected, which was significantly higher than that obtained over clean glass surfaces. Certain organics present on their composition could exert a photo-sensitizing effect that may explain their increased reactivity. Unfortunately, the final balance points towards an important net

  3. Neutralization of methyl cation via chemical reactions in low-energy ion-surface collisions with fluorocarbon and hydrocarbon self-assembled monolayer films.

    Science.gov (United States)

    Somogyi, Arpád; Smith, Darrin L; Wysocki, Vicki H; Colorado, Ramon; Lee, T Randall

    2002-10-01

    Low-energy ion-surface collisions of methyl cation at hydrocarbon and fluorocarbon self-assembled monolayer (SAM) surfaces produce extensive neutralization of CH3+. These experimental observations are reported together with the results obtained for ion-surface collisions with the molecular ions of benzene, styrene, 3-fluorobenzonitrile, 1,3,5-triazine, and ammonia on the same surfaces. For comparison, low-energy gas-phase collisions of CD3+ and 3-fluorobenzonitrile molecular ions with neutral n-butane reagent gas were conducted in a triple quadrupole (QQQ) instrument. Relevant MP2 6-31G*//MP2 6-31G* ab initio and thermochemical calculations provide further insight in the neutralization mechanisms of methyl cation. The data suggest that neutralization of methyl cation with hydrocarbon and fluorocarbon SAMs occurs by concerted chemical reactions, i.e., that neutralization of the projectile occurs not only by a direct electron transfer from the surface but also by formation of a neutral molecule. The calculations indicate that the following products can be formed by exothermic processes and without appreciable activation energy: CH4 (formal hydride ion addition) and C2H6 (formal methyl anion addition) from a hydrocarbon surface and CH3F (formal fluoride addition) from a fluorocarbon surface. The results also demonstrate that, in some cases, simple thermochemical calculations cannot be used to predict the energy profiles because relatively large activation energies can be associated with exothermic reactions, as was found for the formation of CH3CF3 (formal addition of trifluoromethyl anion).

  4. Mechanisms and energetics of surface reactions at the copper-water interface. A critical literature review with implications for the debate on corrosion of copper in anoxic water

    Energy Technology Data Exchange (ETDEWEB)

    Johansson, Adam Johannes; Brinck, Tore [Applied Physical Chemistry, KTH Royal Inst. of Technology, Stockholm (Sweden)

    2012-06-15

    In order to make a critical analysis of the discussion of corrosion of copper in pure anoxic water it is necessary to understand the chemical reactivity at the copper-water interface. Even though the most fundamental issue, i.e. the nature and existence of a hypothetical product that is thermodynamically stable, is still under debate, it is clear that if anoxic corrosion really exists, it must be initiated through oxidative surface reactions at the copper-water interface. This report presents a survey of the peer reviewed literature on the reactivity of copper surfaces in water. Reactions discussed involve molecular adsorption of water, dissociation of the OH-bonds in adsorbed water molecules and hydroxyl groups, the disproportionation/synproportionation equilibrium between hydroxyl groups/hydroxide ions, water molecules and atomic oxygen, the surface diffusion of adsorbed species, and the formation of hydrogen gas (molecular hydrogen). Experimental, as well as theoretical (quantum chemical) studies are reviewed. It is concluded that a limited amount of hydrogen gas (H{sub 2}) should be formed as the result of dissociative water adsorption at certain copper surfaces. Quantitative estimates of the amounts of H2 that could form at the copper-water interface are made. Assuming that the water-cleavage/hydrogen-formation reaction proceeds on an ideal [110] or [100] surface until a hydroxyl monolayer (ML) is reached, the amount of H{sub 2} formed is {approx} 2.4 ng cm{sup -2} copper surface. Based on the literature cited, this is most likely possible, thermodynamically as well as kinetically. Although not proven, it is not unlikely that the reaction can proceed until an oxide ML is formed, which would give 4.8 ng cm{sup -2}. If the formation of an oxide ML is thermodynamically feasible the surface will probably react further, since Cu{sub 2}O(s) is known to activate and cleave the water molecule when it adsorbs at the Cu{sub 2}O(s) surface. Assuming the formation of a

  5. Near-surface clay authigenesis in exhumed fault rock of the Alpine Fault Zone (New Zealand); O-H-Ar isotopic, XRD and chemical analysis of illite and chlorite

    Science.gov (United States)

    Boles, Austin; Mulch, Andreas; van der Pluijm, Ben

    2018-06-01

    Exhumed fault rock of the central Alpine Fault Zone (South Island, New Zealand) shows extensive clay mineralization, and it has been the focus of recent research that aims to describe the evolution and frictional behavior of the fault. Using Quantitative X-ray powder diffraction, 40Ar/39Ar geochronology, hydrogen isotope (δD) geochemistry, and electron microbeam analysis, we constrain the thermal and fluid conditions of deformation that produced two predominant clay phases ubiquitous to the exposed fault damage zone, illite and chlorite. Illite polytype analysis indicates that most end-member illite and chlorite material formed in equilibrium with meteoric fluid (δD = -55 to -75‰), but two locations preserve a metamorphic origin of chlorite (δD = -36 to -45‰). Chlorite chemical geothermometry constrains crystal growth to T = 210-296 °C. Isotopic analysis also constrains illite growth to T < 100 °C, consistent with the mineralogy, with Ar ages <0.5 Ma. High geothermal gradients in the study area promoted widespread, near-surface mineralization, and limited the window of clay authigenesis in the Alpine Fault Zone to <5 km for chlorite and <2 km for illite. This implies a significant contrast between fault rock exposed at the surface and that at depth, and informs discussions about fault strength, clays and frictional behavior.

  6. Detection of uranium extraction zone by axial temperature profiles in a pulsed column for Purex process

    International Nuclear Information System (INIS)

    Tsukada, T.; Takahashi, K.

    1991-01-01

    A new method was presented for detecting uranium extraction zone in a pulsed column by means of measuring axial temperature profile originated from reaction heat during uranium extraction. Key parameters of the temperature profiles were estimated with a code developed for calculating temperature profiles in a direct-contact heat exchanger such as a pulsed column, and were verified using data from a small pulsed column simulating reaction heat with injecting hot water. Finally, the results were compared with those from an actual uranium extraction tests, indicating that the method presented was promising for detecting uranium extraction zone in a pulsed column. (author)

  7. Optimization of remediation strategies using vadose zone monitoring systems

    Science.gov (United States)

    Dahan, Ofer

    2016-04-01

    In-situ bio-remediation of the vadose zone depends mainly on the ability to change the subsurface hydrological, physical and chemical conditions in order to enable development of specific, indigenous, pollutants degrading bacteria. As such the remediation efficiency is much dependent on the ability to implement optimal hydraulic and chemical conditions in deep sections of the vadose zone. These conditions are usually determined in laboratory experiments where parameters such as the chemical composition of the soil water solution, redox potential and water content of the sediment are fully controlled. Usually, implementation of desired optimal degradation conditions in deep vadose zone at full scale field setups is achieved through infiltration of water enriched with chemical additives on the land surface. It is assumed that deep percolation into the vadose zone would create chemical conditions that promote biodegradation of specific compounds. However, application of water with specific chemical conditions near land surface dose not necessarily results in promoting of desired chemical and hydraulic conditions in deep sections of the vadose zone. A vadose-zone monitoring system (VMS) that was recently developed allows continuous monitoring of the hydrological and chemical properties of deep sections of the unsaturated zone. The VMS includes flexible time-domain reflectometry (FTDR) probes which allow continuous monitoring of the temporal variation of the vadose zone water content, and vadose-zone sampling ports (VSPs) which are designed to allow frequent sampling of the sediment pore-water and gas at multiple depths. Implementation of the vadose zone monitoring system in sites that undergoes active remediation provides real time information on the actual chemical and hydrological conditions in the vadose zone as the remediation process progresses. Up-to-date the system has been successfully implemented in several studies on water flow and contaminant transport in

  8. Geotechnology to determine the depth of active zone in expansive ...

    African Journals Online (AJOL)

    Considerable distress to lightly loaded engineered structures in various parts of the coast of Tanzania is due to development of heave and swelling pressure in the active zone of expansive clay soils. The active zone is the region of soil near the surface in which the water content varies due to precipitation and ...

  9. Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce3+ phosphor

    International Nuclear Information System (INIS)

    Kumar, Vinay; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.; Mishra, Varun

    2010-01-01

    The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce 3+ nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm 2 . XPS was used to study the chemical composition of the CaS:Ce 3+ nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO 4 layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO 4 layer on the surface.

  10. Use of Interface Treatment to Reduce Emissions from Residuals in Lower Permeability Zones to Groundwater flowing Through More Permeable Zones (Invited)

    Science.gov (United States)

    Johnson, P.; Cavanagh, B.; Clifton, L.; Daniels, E.; Dahlen, P.

    2013-12-01

    Many soil and groundwater remediation technologies rely on fluid flow for contaminant extraction or reactant delivery (e.g., soil vapor extraction, pump and treat, in situ chemical oxidation, air sparging, enhanced bioremediation). Given that most unconsolidated and consolidated settings have permeability contrasts, the outcome is often preferential treatment of more permeable zones and ineffective treatment of the lower permeability zones. When this happens, post-treatment contaminant emissions from low permeability zone residuals can cause unacceptable long-term impacts to groundwater in the transmissive zones. As complete remediation of the impacted lower permeability zones may not be practicable with conventional technologies, one might explore options that lead to reduction of the contaminant emissions to acceptable levels, rather than full remediation of the lower permeability layers. This could be accomplished either by creating a sustained emission reaction/attenuation zone at the high-low permeability interface, or by creating a clean soil zone extending sufficiently far into the lower permeability layer to cause the necessary reduction in contaminant concentration gradient and diffusive emission. These options are explored in proof-of-concept laboratory-scale physical model experiments. The physical models are prepared with two layers of contrasting permeability and either dissolved matrix storage or nonaqueous phase liquid (NAPL) in the lower permeability layer. A dissolved oxidant is then delivered to the interface via flow across the higher permeability layer and changes in contaminant emissions from the low permeability zone are monitored before, during, and after oxidant delivery. The use of three oxidants (dissolved oxygen, hydrogen peroxide and sodium persulfate) for treatment of emissions from petroleum hydrocarbon residuals is examined.

  11. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  12. Controls of faulting and reaction kinetics on serpentinization and double Benioff zones

    OpenAIRE

    Iyer, Karthik; Rüpke, Lars H.; Phipps Morgan, Jason; Grevemeyer, Ingo

    2012-01-01

    The subduction of partially serpentinized oceanic mantle may potentially be the key geologic process leading to the regassing of Earth's mantle and also has important consequences for subduction zone processes such as element cycling, slab deformation, and intermediate-depth seismicity. However, little is known about the quantity of water that is retained in the slab during mantle serpentinization and the pattern of serpentinization that may occur during bending-related faulting; an initial s...

  13. The effect of mass transport on the graphite/CO2 reaction

    International Nuclear Information System (INIS)

    Stephen, W.J.

    1984-11-01

    The Graphite/CO 2 reaction is strongly inhibited by the reaction product CO and therefore any model for the influence of mass transport on reaction rate should consider this. The problem of internal mass transport alone has been considered in previous notes. This note extends the models to include external mass transport. Results are compared with simple first order reaction with no volume change. The calculations demonstrate that, for strong CO inhibition, external mass transport limits reaction at a much lower rate than for first order kinetics and that the usual concept of three reaction zones corresponding to chemical control, in-pore diffusion control and boundary layer control can be unrealistically idealised. (U.K.)

  14. Temperature-controlled cross-linking of silver nanoparticles with diels-alder reaction and its application on antibacterial property

    Science.gov (United States)

    Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

    2017-05-01

    Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

  15. Cutting Zone Temperature Identification During Machining of Nickel Alloy Inconel 718

    Science.gov (United States)

    Czán, Andrej; Daniš, Igor; Holubják, Jozef; Zaušková, Lucia; Czánová, Tatiana; Mikloš, Matej; Martikáň, Pavol

    2017-12-01

    Quality of machined surface is affected by quality of cutting process. There are many parameters, which influence on the quality of the cutting process. The cutting temperature is one of most important parameters that influence the tool life and the quality of machined surfaces. Its identification and determination is key objective in specialized machining processes such as dry machining of hard-to-machine materials. It is well known that maximum temperature is obtained in the tool rake face at the vicinity of the cutting edge. A moderate level of cutting edge temperature and a low thermal shock reduce the tool wear phenomena, and a low temperature gradient in the machined sublayer reduces the risk of high tensile residual stresses. The thermocouple method was used to measure the temperature directly in the cutting zone. An original thermocouple was specially developed for measuring of temperature in the cutting zone, surface and subsurface layers of machined surface. This paper deals with identification of temperature and temperature gradient during dry peripheral milling of Inconel 718. The measurements were used to identification the temperature gradients and to reconstruct the thermal distribution in cutting zone with various cutting conditions.

  16. Microarray Cluster Analysis of Irradiated Growth Plate Zones Following Laser Microdissection

    International Nuclear Information System (INIS)

    Damron, Timothy A.; Zhang Mingliang; Pritchard, Meredith R.; Middleton, Frank A.; Horton, Jason A.; Margulies, Bryan M.; Strauss, Judith A.; Farnum, Cornelia E.; Spadaro, Joseph A.

    2009-01-01

    Purpose: Genes and pathways involved in early growth plate chondrocyte recovery after fractionated irradiation were sought as potential targets for selective radiorecovery modulation. Materials and Methods: Three groups of six 5-week male Sprague-Dawley rats underwent fractionated irradiation to the right tibiae over 5 days, totaling 17.5 Gy, and then were killed at 7, 11, and 16 days after the first radiotherapy fraction. The growth plates were collected from the proximal tibiae bilaterally and subsequently underwent laser microdissection to separate reserve, perichondral, proliferative, and hypertrophic zones. Differential gene expression was analyzed between irradiated right and nonirradiated left tibia using RAE230 2.0 GeneChip microarray, compared between zones and time points and subjected to functional pathway cluster analysis with real-time polymerase chain reaction to confirm selected results. Results: Each zone had a number of pathways showing enrichment after the pattern of hypothesized importance to growth plate recovery, yet few met the strictest criteria. The proliferative and hypertrophic zones showed both the greatest number of genes with a 10-fold right/left change at 7 days after initiation of irradiation and enrichment of the most functional pathways involved in bone, cartilage, matrix, or skeletal development. Six genes confirmed by real-time polymerase chain reaction to have early upregulation included insulin-like growth factor 2, procollagen type I alpha 2, matrix metallopeptidase 9, parathyroid hormone receptor 1, fibromodulin, and aggrecan 1. Conclusions: Nine overlapping pathways in the proliferative and hypertrophic zones (skeletal development, ossification, bone remodeling, cartilage development, extracellular matrix structural constituent, proteinaceous extracellular matrix, collagen, extracellular matrix, and extracellular matrix part) may play key roles in early growth plate radiorecovery.

  17. Assessing the relationship between surface urban heat islands and landscape patterns across climatic zones in China.

    Science.gov (United States)

    Yang, Qiquan; Huang, Xin; Li, Jiayi

    2017-08-24

    The urban heat island (UHI) effect exerts a great influence on the Earth's environment and human health and has been the subject of considerable attention. Landscape patterns are among the most important factors relevant to surface UHIs (SUHIs); however, the relationship between SUHIs and landscape patterns is poorly understood over large areas. In this study, the surface UHI intensity (SUHII) is defined as the temperature difference between urban and suburban areas, and the landscape patterns are quantified by the urban-suburban differences in several typical landscape metrics (ΔLMs). Temperature and land-cover classification datasets based on satellite observations were applied to analyze the relationship between SUHII and ΔLMs in 332 cities/city agglomerations distributed in different climatic zones of China. The results indicate that SUHII and its correlations with ΔLMs are profoundly influenced by seasonal, diurnal, and climatic factors. The impacts of different land-cover types on SUHIs are different, and the landscape patterns of the built-up and vegetation (including forest, grassland, and cultivated land) classes have the most significant effects on SUHIs. The results of this study will help us to gain a deeper understanding of the relationship between the SUHI effect and landscape patterns.

  18. Urban Imperviousness Effects on Summer Surface Temperatures Nearby Residential Buildings in Different Urban Zones of Parma

    Directory of Open Access Journals (Sweden)

    Marco Morabito

    2017-12-01

    Full Text Available Rapid and unplanned urban growth is responsible for the continuous conversion of green or generally natural spaces into artificial surfaces. The high degree of imperviousness modifies the urban microclimate and no studies have quantified its influence on the surface temperature (ST nearby residential building. This topic represents the aim of this study carried out during summer in different urban zones (densely urbanized or park/rural areas of Parma (Northern Italy. Daytime and nighttime ASTER images, the local urban cartography and the Italian imperviousness databases were used. A reproducible/replicable framework was implemented named “Building Thermal Functional Area” (BTFA useful to lead building-proxy thermal analyses by using remote sensing data. For each residential building (n = 8898, the BTFA was assessed and the correspondent ASTER-LST value (ST_BTFA and the imperviousness density were calculated. Both daytime and nighttime ST_BTFA significantly (p < 0.001 increased when high levels of imperviousness density surrounded the residential buildings. These relationships were mostly consistent during daytime and in densely urbanized areas. ST_BTFA differences between urban and park/rural areas were higher during nighttime (above 1 °C than daytime (about 0.5 °C. These results could help to identify “urban thermal Hot-Spots” that would benefit most from mitigation actions.

  19. Enzymatic Transesterification of Ethyl Ferulate with Fish Oil and Reaction Optimization by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Zhiyong Yang

    2012-01-01

    Full Text Available The enzymatic transesterification of ethyl ferulate (EF with fish oil from cod liver was investigated with Novozym® 435 as catalyst under solvent-free conditions. The purpose of the study is to evaluate the synthesis system for the production of feruloyl fish oil in industry. The modified HPLC method was first set up to characterise the reaction products together with liquid chromatography electrospray time-of-flight mass spectrometry (HPLC-ESI-TOF-MS. The influence of the addition of glycerol to the system on the feruloyl acylglycerol profile was investigated in terms of transesterification performance. The bioconversion rate of EF can be significantly increased with the increased formation of feruloyl fish oil products when appropriate amount of glycerol is present in the reaction. Therefore, an equivalent molar amount of glycerol was added to EF for the practical optimization of the system. The mutual effects of temperature (40 to 70 °C, reaction time (1 to 5 days, enzyme load (2 to 20 % and molar ratio of fish oil and EF in the substrate (1 to 5 were thus studied with the assistance of response surface methodology (RSM for the purpose of maximizing the formation of feruloyl fish oil. The models were well fitted and verified. The optimized conditions were found to be: temperature 70 °C, enzyme load 4.3 %, substrate ratio 4.7, and reaction time 5 days. Under these conditions, the maximum conversion of EF reached 92.4 %, and the formation of feruloyl fish oil reached 80.4 %, but the formation of by-product was minimized to 11.4 % only.

  20. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. © 2013 American Chemical Society.

  1. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Directory of Open Access Journals (Sweden)

    A. D. Elvidge

    2016-02-01

    Full Text Available Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol–Cloud Coupling And Climate Interactions in the Arctic (ACCACIA project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10 from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85  ×  10−3. CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012 tailored for sea-ice drag over the MIZ in which the two constituent components of drag – skin and form drag – are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012 scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values – especially at the higher ice fractions – than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on

  2. Procedure for the gasification of pelletized carbonaceous fuels

    Energy Technology Data Exchange (ETDEWEB)

    Ban, T.E.; Sheppard, J.C.; Marlowe, W.H.

    1980-08-07

    A continuous, travelling grate device is used for the production of low Btu gas with high hydrogen and carbon monoxide content from coke pellets. For the initiation of an oxidation zone the surface of one of the layers of a horizontally moved coal bed with a layer of a sorted recycled coal charge and a layer of fresh coal is ignited. The zone migrates in the form of a wave into the lower and upper layer reducing the coal which is to be found in zones in front of the forward migrating oxidation zones. The reactions are stopped before the reaction zones reaches the both extreme surfaces of the beds.

  3. Vadose zone studies at an industrial contaminated site: the vadose zone monitoring system and cross-hole geophysics

    Science.gov (United States)

    Fernandez de Vera, Natalia; Beaujean, Jean; Jamin, Pierre; Nguyen, Frédéric; Dahan, Ofer; Vanclooster, Marnik; Brouyère, Serge

    2014-05-01

    installed in two slanted boreholes on site, together with four vertical boreholes containing electrodes for geophysical measurements. Currently the site is being monitored under natural recharge conditions. Initial results show the reaction of the vadose zone to rainfall events, as well as chemical evolution of soil water with depth.

  4. Energy balance and flow in steam generator part with sodium-water reaction

    International Nuclear Information System (INIS)

    Matal, O.

    1980-01-01

    Relations were derived for the calculation of heat liberated during the sodium water reaction in a tube failure in different parts of a steam generator. The results are graphically shown in i-T diagrams. Heat removal is described from the reaction zone to water and steam in undisturbed tubes and to the steam generator metal structure. (author)

  5. Hyporheic Microbes Database - Microbes in the hyporheic zone

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The hyporheic zone (i.e., where surface & groundwater converge) is a geomorphic feature that contributes to the overall health of streams & rivers. Much of...

  6. Active Deformation of Malawi Rift's North Basin Hinge Zone Modulated by Reactivation of Preexisting Precambrian Shear Zone Fabric

    Science.gov (United States)

    Kolawole, F.; Atekwana, E. A.; Laó-Dávila, D. A.; Abdelsalam, M. G.; Chindandali, P. R.; Salima, J.; Kalindekafe, L.

    2018-03-01

    We integrated temporal aeromagnetic data and recent earthquake data to address the long-standing question on the role of preexisting Precambrian structures in modulating strain accommodation and subsequent ruptures leading to seismic events within the East African Rift System. We used aeromagnetic data to elucidate the relationship between the locations of the 2009 Mw 6.0 Karonga, Malawi, earthquake surface ruptures and buried basement faults along the hinge zone of the half-graben comprising the North Basin of the Malawi Rift. Through the application of derivative filters and depth-to-magnetic-source modeling, we identified and constrained the trend of the Precambrian metamorphic fabrics and correlated them to the three-dimensional structure of buried basement faults. Our results reveal an unprecedented detail of the basement fabric dominated by high-frequency WNW to NW trending magnetic lineaments associated with the Precambrian Mughese Shear Zone fabric. The high-frequency magnetic lineaments are superimposed by lower frequency NNW trending magnetic lineaments associated with possible Cenozoic faults. Surface ruptures associated with the 2009 Mw 6.0 Karonga earthquake swarm aligned with one of the NNW-trending magnetic lineaments defining a normal fault that is characterized by right-stepping segments along its northern half and coalesced segments on its southern half. Fault geometries, regional kinematics, and spatial distribution of seismicity suggest that seismogenic faults reactivated the basement fabric found along the half-graben hinge zone. We suggest that focusing of strain accommodation and seismicity along the half-graben hinge zone is facilitated and modulated by the presence of the basement fabric.

  7. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

    Science.gov (United States)

    Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal

  8. The Effectiveness of Surface Coatings on Preventing Interfacial Reaction During Ultrasonic Welding of Aluminum to Magnesium

    Science.gov (United States)

    Panteli, Alexandria; Robson, Joseph D.; Chen, Ying-Chun; Prangnell, Philip B.

    2013-12-01

    High power ultrasonic spot welding (USW) is a solid-state joining process that is advantageous for welding difficult dissimilar material couples, like magnesium to aluminum. USW is also a useful technique for testing methods of controlling interfacial reaction in welding as the interface is not greatly displaced by the process. However, the high strain rate deformation in USW has been found to accelerate intermetallic compound (IMC) formation and a thick Al12Mg17 and Al3Mg2 reaction layer forms after relatively short welding times. In this work, we have investigated the potential of two approaches for reducing the IMC reaction rate in dissimilar Al-Mg ultrasonic welds, both involving coatings on the Mg sheet surface to (i) separate the join line from the weld interface, using a 100- μm-thick Al cold spray coating, and (ii) provide a diffusion barrier layer, using a thin manganese physical vapor deposition (PVD) coating. Both methods were found to reduce the level of reaction and increase the failure energy of the welds, but their effectiveness was limited due to issues with coating attachment and survivability during the welding cycle. The effect of the coatings on the joint's interface microstructure, and the fracture behavior have been investigated in detail. Kinetic modeling has been used to show that the benefit of the cold spray coating can be attributed to the reaction rate reverting to that expected under static conditions. This reduces the IMC growth rate by over 50 pct because at the weld line, the high strain rate dynamic deformation in USW normally enhances diffusion through the IMC layer. In comparison, the thin PVD barrier coating was found to rapidly break up early in USW and become dispersed throughout the deformation layer reducing its effectiveness.

  9. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  10. Photocatalysis reaction on ordered arrays of Au nanorads with controlled orientations

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Min Jung; Han, Sang Woo [Dept. of Chemistry and KI for the NanoCentury, KAIST, Daejeon (Korea, Republic of)

    2015-03-15

    Surface photocatalysis reactions of aromatic compounds self-assembled on metal surfaces have been extensively explored for the past decades. Despite the numerous studies on the surface photocatalysis reactions of aromatic compounds, that on Au surface has rarely been reported due to the inefficiency of Au toward these reactions compared to Ag. The detailed experimental and theoretical studies on the mechanism of the enhanced photocatalytic function of the AuNR arrays are currently underway.

  11. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  12. Fault zone architecture, San Jacinto fault zone, southern California: evidence for focused fluid flow and heat transfer in the shallow crust

    Science.gov (United States)

    Morton, N.; Girty, G. H.; Rockwell, T. K.

    2011-12-01

    We report results of a new study of the San Jacinto fault zone architecture in Horse Canyon, SW of Anza, California, where stream incision has exposed a near-continuous outcrop of the fault zone at ~0.4 km depth. The fault zone at this location consists of a fault core, transition zone, damage zone, and lithologically similar wall rocks. We collected and analyzed samples for their bulk and grain density, geochemical data, clay mineralogy, and textural and modal mineralogy. Progressive deformation within the fault zone is characterized by mode I cracking, subsequent shearing of already fractured rock, and cataclastic flow. Grain comminution advances towards the strongly indurated cataclasite fault core. Damage progression towards the core is accompanied by a decrease in bulk and grain density, and an increase in porosity and dilational volumetric strain. Palygorskite and mixed-layer illite/smectite clay minerals are present in the damage and transition zones and are the result of hydrolysis reactions. The estimated percentage of illite in illite/smectite increases towards the fault core where the illite/smectite to illite conversion is complete, suggesting elevated temperatures that may have reached 150°C. Chemical alteration and elemental mass changes are observed throughout the fault zone and are most pronounced in the fault core. We conclude that the observed chemical and mineralogical changes can only be produced by the interaction of fractured wall rocks and chemically active fluids that are mobilized through the fault zone by thermo-pressurization during and after seismic events. Based on the high element mobility and absence of illite/smectite in the fault core, we expect that greatest water/rock ratios occur within the fault core. These results indicate that hot pore fluids circulate upwards through the fractured fault core and into the surrounding damage zone. Though difficult to constrain, the site studied during this investigation may represent the top

  13. COLLOID-FACILITATED TRANSPORT OF RADIONUCLIDES THROUGH THE VADOSE ZONE

    International Nuclear Information System (INIS)

    Flury, Markus

    2003-01-01

    Contaminants have leaked into the vadose zone at the USDOE Hanford reservation. It is important to understand the fate and transport of these contaminants to design remediation strategies and long-term waste management plans at the Hanford reservation. Colloids may play an important role in fate and transport of strongly sorbing contaminants, such as Cs or Pu. This project seeks to improve the basic understanding of colloid and colloid-facilitated transport of contaminants in the vadose zone. The specific objectives addressed are: (1) Determine the structure, composition, and surface charge characteristics of colloidal particles formed under conditions similar to those occurring during leakage of waste typical of Hanford tank supernatants into soils and sediments surrounding the tanks. (2) Characterize the mutual interactions between colloids, contaminant, and soil matrix in batch experiments under various ionic strength and pH conditions. We will investigate the nature of the solid-liquid interactions and the kinetics of the reactions. (3) Evaluate mobility of colloids through soil under different degrees of water saturation and solution chemistry (ionic strength and pH). (4) Determine the potential of colloids to act as carriers to transport the contaminant through the vadose zone and verify the results through comparison with field samples collected under leaking tanks. (5) Improve conceptual characterization of colloid-contaminant-soil interactions and colloid-facilitated transport for implementation into reactive chemical transport models. This project was in part supported by an NSF-IGERT grant to Washington State University. The IGERT grant provided funding for graduate student research and education, and two graduate students were involved in the EMSP project. The IGERT program also supported undergraduate internships. The project is part of a larger EMSP program to study fate and transport of contaminants under leaking Hanford waste tanks. The project has

  14. A Microfluidic Chip Based on Localized Surface Plasmon Resonance for Real-Time Monitoring of Antigen-Antibody Reactions

    Science.gov (United States)

    Hiep, Ha Minh; Nakayama, Tsuyoshi; Saito, Masato; Yamamura, Shohei; Takamura, Yuzuru; Tamiya, Eiichi

    2008-02-01

    Localized surface plasmon resonance (LSPR) connecting to noble metal nanoparticles is an important issue for many analytical and biological applications. Therefore, the development of microfluidic LSPR chip that allows studying biomolecular interactions becomes an essential requirement for micro total analysis systems (µTAS) integration. However, miniaturized process of the conventional surface plasmon resonance system has been faced with some limitations, especially with the usage of Kretschmann configuration in total internal reflection mode. In this study, we have tried to solve this problem by proposing a novel microfluidic LSPR chip operated with a simple collinear optical system. The poly(dimethylsiloxane) (PDMS) based microfluidic chip was fabricated by soft-lithography technique and enables to interrogate specific insulin and anti-insulin antibody reaction in real-time after immobilizing antibody on its surface. Moreover, the sensing ability of microfluidic LSPR chip was also evaluated with various glucose concentrations. The kinetic constant of insulin and anti-insulin antibody was determined and the detection limit of 100 ng/mL insulin was archived.

  15. The Role of Surface Protection for High-Temperature Performance of TiAl Alloys

    Science.gov (United States)

    Schütze, Michael

    2017-12-01

    In the temperature range where TiAl alloys are currently being used in jet engine and automotive industries, surface reaction with the operating environment is not yet a critical issue. Surface treatment may, however, be needed in order to provide improved abrasion resistance. Development routes currently aim at a further increase in operation temperatures in gas turbines up to 800°C and higher, and in automotive applications for turbocharger rotors, even up to 1050°C. In this case, oxidation rates may reach levels where significant metal consumption of the load-bearing cross-section can occur. Another possibly even more critical issue can be high-temperature-induced oxygen and nitrogen up-take into the metal subsurface zone with subsequent massive ambient temperature embrittlement. Solutions for these problems are based on a deliberate phase change of the metal subsurface zone by diffusion treatments and by using effects such as the halogen effect to change the oxidation mechanism at high temperatures. Other topics of relevance for the use of TiAl alloys in high-temperature applications can be high-temperature abrasion resistance, thermal barrier coatings on TiAl and surface quality in additive manufacturing, in all these cases-focusing on the role of the operation environment. This paper addresses the recent developments in these areas and the requirements for future work.

  16. Conceptual Model of Uranium in the Vadose Zone for Acidic and Alkaline Wastes Discharged at the Hanford Site Central Plateau

    Energy Technology Data Exchange (ETDEWEB)

    Truex, Michael J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Szecsody, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qafoku, Nikolla [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Serne, R. Jeffrey [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2014-09-01

    Historically, uranium was disposed in waste solutions of varying waste chemistry at the Hanford Site Central Plateau. The character of how uranium was distributed in the vadose zone during disposal, how it has continued to migrate through the vadose zone, and the magnitude of potential impacts on groundwater are strongly influenced by geochemical reactions in the vadose zone. These geochemical reactions can be significantly influenced by the disposed-waste chemistry near the disposal location. This report provides conceptual models and supporting information to describe uranium fate and transport in the vadose zone for both acidic and alkaline wastes discharged at a substantial number of waste sites in the Hanford Site Central Plateau. The conceptual models include consideration of how co-disposed acidic or alkaline fluids influence uranium mobility in terms of induced dissolution/precipitation reactions and changes in uranium sorption with a focus on the conditions near the disposal site. This information, when combined with the extensive information describing uranium fate and transport at near background pH conditions, enables focused characterization to support effective fate and transport estimates for uranium in the subsurface.

  17. Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

    International Nuclear Information System (INIS)

    Frisch, M.J.; Binkley, J.S.; Schaefer, H.F. III

    1984-01-01

    The relative energies of the stationary points on the FH 2 and H 2 CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H 2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Moller--Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H 2 →FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol -1 of the experimental value using the largest basis set considered. The qualitative features of the H 2 CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended

  18. Bone reactions adjacent to titanium implants with different surface characteristics subjected to static load. A study in the dog (II)

    DEFF Research Database (Denmark)

    Gotfredsen, K; Berglundh, T; Lindhe, J

    2001-01-01

    The purpose of the present study was to compare bone reactions adjacent to titanium implants with either a titanium plasma-sprayed (TPS) or a machined surface subjected to lateral static loading induced by an expansion force. In 3 labrador dogs, the 2nd, 3rd and 4th mandibular premolars were...

  19. Petrography study on altered flint aggregate by alkali-silica reaction

    International Nuclear Information System (INIS)

    Bulteel, D.; Rafai, N.; Degrugilliers, P.; Garcia-Diaz, E.

    2004-01-01

    The aim of our study is to improve our understanding of an alkali-silica reaction (ASR) via petrography. We used a chemical concrete subsystem: flint aggregate, portlandite and KOH. The altered flint aggregate is followed by optical microscopy and scanning electron microscopy (SEM) before and after acid treatment at different intervals. After acid treatment, the observations showed an increase in aggregate porosity and revealed internal degradation of the aggregate. This degradation created amorphous zones. Before acid treatment, the analyses on polished sections by scanning electron microscopy coupled with energy dispersive spectroscopy (EDS) enabled visualization of K + and Ca 2+ penetration into the aggregate. The appearance of amorphous zones and penetration of positive ions into the aggregate are correlated with the increase in the molar fraction of silanol sites. This degradation is specific to the alkali-silica reaction

  20. Large scale multi-zone creep finite element modelling of a main steam line branch intersection

    International Nuclear Information System (INIS)

    Payten, Warwick

    2006-01-01

    A number of papers detail the non-linear creep finite element analysis of branch pieces. Predominately these models have incorporated only a single material zone representing the parent material. Multi-zone models incorporating weld material and heat affected zones have primarily been two-dimensional analyses, in part due to the large number of elements required to adequately represent all of the zones. This paper describes a non-linear creep analysis of a main steam line branch intersection using creep properties to represent the parent metal, weld metal, and heat affected zone (HAZ), the stress redistribution over 100,000 h is examined. The results show that the redistribution leads to a complex stress state, particularly at the heat affected zone. Although, there is damage on the external surface of the branch piece as expected, the results indicate that the damage would be more widespread through extensive sections of the heat affected zone. This would appear to indicate that the time between damage indications on the surface using techniques such as replication and full thickness damage may be more limited then previously expected

  1. Laser thermal effect on silicon nitride ceramic based on thermo-chemical reaction with temperature-dependent thermo-physical parameters

    International Nuclear Information System (INIS)

    Pan, A.F.; Wang, W.J.; Mei, X.S.; Wang, K.D.; Zhao, W.Q.; Li, T.Q.

    2016-01-01

    Highlights: • A two-dimensional thermo-chemical reaction model is creatively built. • Thermal conductivity and heat capacity of β-Si_3N_4 are computed accurately. • The appropriate thermo-chemical reaction rate is fitted and reaction element length is set to assure the constringency. • The deepest ablated position was not the center of the ablated area due to plasma absorption. • The simulation results demonstrate the thermo-chemical process cant be simplified to be physical phase transition. - Abstract: In this study, a two-dimensional thermo-chemical reaction model with temperature-dependent thermo-physical parameters on Si_3N_4 with 10 ns laser was developed to investigate the ablated size, volume and surface morphology after single pulse. For model parameters, thermal conductivity and heat capacity of β-Si_3N_4 were obtained from first-principles calculations. Thermal-chemical reaction rate was fitted by collision theory, and then, reaction element length was deduced using the relationship between reaction rate and temperature distribution. Furthermore, plasma absorption related to energy loss was approximated as a function of electron concentration in Si_3N_4. It turned out that theoretical ablated volume and radius increased and then remained constant with increasing laser energy, and the maximum ablated depth was not in the center of the ablated zone. Moreover, the surface maximum temperature of Si_3N_4 was verified to be above 3000 K within pulse duration, and it was much higher than its thermal decomposition temperature of 1800 K, which indicated that Si_3N_4 was not ablated directly above the thermal decomposition temperature. Meanwhile, the single pulse ablation of Si_3N_4 was performed at different powers using a TEM_0_0 10 ns pulse Nd:YAG laser to validate the model. The model showed a satisfactory consistence between the experimental data and numerical predictions, presenting a new modeling technology that may significantly increase the

  2. Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.

    Science.gov (United States)

    Finlayson-Pitts, Barbara J

    2009-09-28

    While particles have significant deleterious impacts on human health, visibility and climate, quantitative understanding of their formation, composition and fates remains problematic. Indeed, in many cases, even qualitative understanding is lacking. One area of particular uncertainty is the nature of particle surfaces and how this determines interactions with gases in the atmosphere, including water, which is important for cloud formation and properties. The focus in this Perspective article is on some chemistry relevant to airborne particles and especially to reactions occurring on their surfaces. The intent is not to provide a comprehensive review, but rather to highlight a few selected examples of interface chemistry involving inorganic and organic species that may be important in the lower atmosphere. This includes sea salt chemistry, nitrate and nitrite ion photochemistry, organics on surfaces and heterogeneous reactions of oxides of nitrogen on proxies for airborne mineral dust and boundary layer surfaces. Emphasis is on the molecular level understanding that can only be gained by fully integrating experiment and theory to elucidate these complex systems.

  3. Karst system vadose zone hydrodynamics highlighted by an integrative geophysical and hydrogeological monitoring

    Science.gov (United States)

    Watlet, A.; Van Camp, M. J.; Francis, O.; Poulain, A.; Hallet, V.; Rochez, G.; Kaufmann, O.

    2015-12-01

    The vadose zone of karst systems plays an important role on the water dynamics. In particular, temporary perched aquifers can appear in the subsurface due to changes of climate conditions, diminished evapotranspiration and differences of porosity relative to deeper layers. It is therefore crucial, but challenging, to separate the hydrological signature of the vadose zone from the one of the saturated zone for understanding hydrological processes that occur in the vadose zone. Although many difficulties are usually encountered when studying karst environments due to their heterogeneities, cave systems offer an outstanding opportunity to investigate vadose zone from the inside with various techniques. We present results covering two years of hydrogeological and geophysical monitoring at the Rochefort Cave Laboratory (RCL), located in the Variscan fold-and-thrust belt (Belgium), a region that shows many karstic networks within Devonian limestone units. Hydrogeological data such as flows and levels monitoring or tracer tests performed in both vadose and saturated zones bring valuable information on the hydrological context of the studied area. Combining those results with geophysical measurements allows validating and imaging them with more integrative techniques. A microgravimetric monitoring involves a superconducting gravimeter continuously measuring at the surface of the RCL. Early in 2015, a second relative gravimeter was installed in the underlying cave system located 35 meters below the surface. This set up allows highlighting vadose gravity changes. These relative measurements are calibrated using an absolute gravimeter. 12 additional stations (7 at the surface, 5 in the cave) are monitored on a monthly basis by a spring gravimeter. To complete these gravimetric measurements, the site has been equipped with a permanent Electrical Resistivity Tomography (ERT) monitoring system comprising an uncommon array of surface, borehole and cave electrodes. Although such

  4. The chemistry of the carbothermal synthesis of β-SiC : reaction mechanism, reaction rate and grain growth

    NARCIS (Netherlands)

    van Dijen, F.K.; Metselaar, R.

    1991-01-01

    Evidence is given that in the present case the reaction mechanism of ß-SiC formation from silica and carbon is a direct solid-state reaction in which silica migrates over the silicon carbide surface to the carbon. A high value (440 kJ/mol) of activation energy is obtained for this reaction. This

  5. Accurate numerical simulation of reaction-diffusion processes for heavy oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Govind, P.A.; Srinivasan, S. [Society of Petroleum Engineers, Richardson, TX (United States)]|[Texas Univ., Austin, TX (United States)

    2008-10-15

    This study evaluated a reaction-diffusion simulation tool designed to analyze the displacement of carbon dioxide (CO{sub 2}) in a simultaneous injection of carbon dioxide and elemental sodium in a heavy oil reservoir. Sodium was used due to the exothermic reaction of sodium with in situ that occurs when heat is used to reduce oil viscosity. The process also results in the formation of sodium hydroxide that reduces interfacial tension at the bitumen interface. A commercial simulation tool was used to model the sodium transport mechanism to the reaction interface through diffusion as well as the reaction zone's subsequent displacement. The aim of the study was to verify if the in situ reaction was able to generate sufficient heat to reduce oil viscosity and improve the displacement of the heavy oil. The study also assessed the accuracy of the reaction front simulation tool, in which an alternate method was used to model the propagation front as a moving heat source. The sensitivity of the simulation results were then evaluated in relation to the diffusion coefficient in order to understand the scaling characteristics of the reaction-diffusion zone. A pore-scale simulation was then up-scaled to grid blocks. Results of the study showed that when sodium suspended in liquid CO{sub 2} is injected into reservoirs, it diffuses through the carrier phase and interacts with water. A random walk diffusion algorithm with reactive dissipation was implemented to more accurately characterize reaction and diffusion processes. It was concluded that the algorithm modelled physical dispersion while neglecting the effect of numerical dispersion. 10 refs., 3 tabs., 24 figs.

  6. Earthquakes, fluid pressures and rapid subduction zone metamorphism

    Science.gov (United States)

    Viete, D. R.

    2013-12-01

    High-pressure/low-temperature (HP/LT) metamorphism is commonly incomplete, meaning that large tracts of rock can remain metastable at blueschist- and eclogite-facies conditions for timescales up to millions of years [1]. When HP/LT metamorphism does take place, it can occur over extremely short durations (the role of fluids in providing heat for metamorphism [2] or catalyzing metamorphic reactions [1]. Earthquakes in subduction zone settings can occur to depths of 100s of km. Metamorphic dehydration and the associated development of elevated pore pressures in HP/LT metamorphic rocks has been identified as a cause of earthquake activity at such great depths [3-4]. The process of fracturing/faulting significantly increases rock permeability, causing channelized fluid flow and dissipation of pore pressures [3-4]. Thus, deep subduction zone earthquakes are thought to reflect an evolution in fluid pressure, involving: (1) an initial increase in pore pressure by heating-related dehydration of subduction zone rocks, and (2) rapid relief of pore pressures by faulting and channelized flow. Models for earthquakes at depth in subduction zones have focussed on the in situ effects of dehydration and then sudden escape of fluids from the rock mass following fracturing [3-4]. On the other hand, existing models for rapid and incomplete metamorphism in subduction zones have focussed only on the effects of heating and/or hydration with the arrival of external fluids [1-2]. Significant changes in pressure over very short timescales should result in rapid mineral growth and/or disequilibrium texture development in response to overstepping of mineral reaction boundaries. The repeated process of dehydration-pore pressure development-earthquake-pore pressure relief could conceivably produce a record of episodic HP/LT metamorphism driven by rapid pressure pulses. A new hypothesis is presented for the origins of HP/LT metamorphism: that HP/LT metamorphism is driven by effective pressure

  7. Plutonium Particle Migration in the Shallow Vadose Zone: The Nevada Test Site as an Analog Site

    Science.gov (United States)

    Hunt, J. R.; Smith, D. K.

    2004-12-01

    The upper meter of the vadose zone in desert environments is the horizon where wastes have been released and human exposure is determined through dermal, inhalation, and food uptake pathways. This region is also characterized by numerous coupled processes that determine contaminant transport, including precipitation infiltration, evapotranspiration, daily and annual temperature cycling, dust resuspension, animal burrowing, and geochemical weathering reactions. While there is considerable interest in colloidal transport of minerals, pathogenic organisms, and contaminants in the vadose zone, there are limited field sites where the actual occurrence of contaminant migration can be quantified over the appropriate spatial and temporal scales of interest. At the US Department of Energy Nevada Test Site, there have been numerous releases of radionuclides since the 1950's that have become field-scale tracer tests. One series of tests was the four safety shots conducted in an alluvial valley of Area 11 in the 1950's. These experiments tested the ability of nuclear materials to survive chemical explosions without initiating fission reactions. Four above-ground tests were conducted and they released plutonium and uranium on the desert valley floor with only one of the tests undergoing some fission. Shortly after the tests, the sites were surveyed for radionuclide distribution on the land surface using aerial surveys and with depth. Additional studies were conducted in the 1970's to better understand the fate of plutonium in the desert that included studies of depth distribution and dust resuspension. More recently, plutonium particle distribution in the soil profile was detected using autoradiography. The results to date demonstrate the vertical migration of plutonium particles to depths in excess of 30 cm in this arid vadose zone. While plutonium migration at the Nevada Test Site has been and continues to be a concern, these field experiments have become analog sites for the

  8. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  9. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  10. An integrated high temperature environmental cell for atom probe tomography studies of gas-surface reactions: Instrumentation and results

    International Nuclear Information System (INIS)

    Dumpala, S.; Broderick, S.R.; Bagot, P.A.J.; Rajan, K.

    2014-01-01

    An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument. - Highlights: • Designed and built atom probe environmental cell for in situ reactions. • Investigated Al oxidation, and demonstrated improvement with new cell. • in situ APT analysis of Pt-alloys showed surface segregation of Rh and Ir

  11. Habitable zone limits for dry planets.

    Science.gov (United States)

    Abe, Yutaka; Abe-Ouchi, Ayako; Sleep, Norman H; Zahnle, Kevin J

    2011-06-01

    Most discussion of habitable planets has focused on Earth-like planets with globally abundant liquid water. For an "aqua planet" like Earth, the surface freezes if far from its sun, and the water vapor greenhouse effect runs away if too close. Here we show that "land planets" (desert worlds with limited surface water) have wider habitable zones than aqua planets. For planets at the inner edge of the habitable zone, a land planet has two advantages over an aqua planet: (i) the tropics can emit longwave radiation at rates above the traditional runaway limit because the air is unsaturated and (ii) the dry air creates a dry stratosphere that limits hydrogen escape. At the outer limits of the habitable zone, the land planet better resists global freezing because there is less water for clouds, snow, and ice. Here we describe a series of numerical experiments using a simple three-dimensional global climate model for Earth-sized planets. Other things (CO(2), rotation rate, surface pressure) unchanged, we found that liquid water remains stable at the poles of a low-obliquity land planet until net insolation exceeds 415 W/m(2) (170% that of modern Earth), compared to 330 W/m(2) (135%) for the aqua planet. At the outer limits, we found that a low-obliquity land planet freezes at 77%, while the aqua planet freezes at 90%. High-obliquity land and aqua planets freeze at 58% and 72%, respectively, with the poles offering the last refuge. We show that it is possible that, as the Sun brightens, an aqua planet like Earth can lose most of its hydrogen and become a land planet without first passing through a sterilizing runaway greenhouse. It is possible that Venus was a habitable land planet as recently as 1 billion years ago.

  12. Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

    DEFF Research Database (Denmark)

    Binning, Philip John; Postma, Diederik Jan; Russel, T.F.

    2007-01-01

    Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed at...... parameters; for example, the time to approach steady state depends exponentially on the distance between the soil surface and the subsurface reactive zone. Copyright 2007 by the American Geophysical Union....... at depth in the unsaturated zone, a pressure gradient is created between the reactive zone and the ground surface, causing a substantial advective air flow into the subsurface. To determine the balance between advective and diffusive transport, a one-dimensional multicomponent unsaturated zone gas...

  13. Transfusion reaction - hemolytic

    Science.gov (United States)

    ... Names Blood transfusion reaction Images Surface proteins causing rejection References Choate JD, Maitta RW, Tormey CA, Wu ... PA: Elsevier Saunders; 2016:chap 177. Hall JE. Blood types; transfusion; tissue and organ transplantation. In: Hall JE, ...

  14. IODP expedition 334: An investigation of the sedimentary record, fluid flow and state of stress on top of the seismogenic zone of an erosive subduction margin

    Digital Repository Service at National Institute of Oceanography (India)

    Vannucchi, P.; Ujiie, K.; Stroncik, N.; IODP Exp. 334 Scientific Party; Yatheesh, V.

    permeable horizons in the upper plate may record reactions occurring at greater depths in the subduction zone and can be used to constrain reactions occurring within the seismogenic zone (Vannucchi et al., 2010). Based on the first results obtained during... of modified seawater in the igneous basement could be identified. Whereas pore fluids in the uppermost ~50 m at all sites drilled during Exp. 334 were dominated by reactions associated with the cycling of organic carbon, deep fluid flow was also detected...

  15. Automated spectral zones selection methodology for diffusion theory data preparation for pebble bed reactor analysis

    Science.gov (United States)

    Mphahlele, Ramatsemela

    A methodology is developed for the determination of the optimum spectral zones in Pebble Bed Reactors (PBR). In this work a spectral zone is defined as a zone made up of a number of nodes whose characteristics are collectively similar and that are assigned the same few-group diffusion constants. In other words the spectral zones are the regions over which the few-group diffusion parameters are generated. The identification of spectral boundaries is treated as an optimization problem. It is solved by systematically and simultaneously repositioning all zone boundaries to achieve the global minimum error between the reference transport solution (MCNP) and the diffusion code solution (NEM). The objective function for the optimization algorithm is the total reaction rate error, which is defined as the sum of the leakage, absorption and fission reaction rates error in each zone. An iterative determination of group-dependent bucklings is incorporated into the methodology to properly account for spectral effects of neighboring zones. A preferred energy group structure has also been chosen. This optimization approach with the reference transport solution has proved to be accurate and consistent, however the computational effort required to complete the optimization process is significant. Thus a more practical methodology is also developed for the determination of the spectral zones in PBRs. The reactor physics characteristics of the spectral zones have been studied to understand the nature of the spectral zone boundaries. The practical tool involves the use of spectral indices based on few-group diffusion theory whole core calculations. With this methodology, there is no need to first have a reference transport solution. It is shown that the diffusion-theory coarse group fluxes and the effective multiplication factor computed using zones based on the practical index agrees within a narrow tolerance with those of the reference approach. Therefore the "practical" index

  16. Reactions of sulphur mustard on impregnated carbons.

    Science.gov (United States)

    Prasad, G K; Singh, Beer

    2004-12-31

    Activated carbon of surface area 1100 m2/gm is impregnated with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 degrees C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO3/C system, whereas on NaOH/CrO3/EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO3)2/C system it gave hemisulphur mustard and thiodiglycol. On RuCl3/C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard.

  17. Reactions of sulphur mustard on impregnated carbons

    International Nuclear Information System (INIS)

    Prasad, G.K.; Singh, Beer

    2004-01-01

    Activated carbon of surface area 1100 m 2 /gm is impregnated with 4% sodium hydroxide plus 3% Cr(Vi) as CrO 3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 deg. C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO 3 /C system, whereas on NaOH/CrO 3 /EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO 3 ) 2 /C system it gave hemisulphur mustard and thiodiglycol. On RuCl 3 /C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard

  18. 33 CFR 165.709 - Security Zone; Charleston Harbor, Cooper River, South Carolina.

    Science.gov (United States)

    2010-07-01

    ..., Cooper River, South Carolina. 165.709 Section 165.709 Navigation and Navigable Waters COAST GUARD... § 165.709 Security Zone; Charleston Harbor, Cooper River, South Carolina. (a) Regulated area. The Coast Guard is establishing a fixed security zone on all waters of the Cooper River, bank-to-bank and surface...

  19. Reflection seismic methods applied to locating fracture zones in crystalline rock

    International Nuclear Information System (INIS)

    Juhlin, C.

    1998-01-01

    The reflection seismic method is a potentially powerful tool for identifying and localising fracture zones in crystalline rock if used properly. Borehole sonic logs across fracture zones show that they have reduced P-wave velocities compared to the surrounding intact rock. Diagnostically important S-wave velocity log information across the fracture zones is generally lacking. Generation of synthetic reflection seismic data and subsequent processing of these data show that structures dipping up towards 70 degrees from horizontal can be reliably imaged using surface seismic methods. Two real case studies where seismic reflection methods have been used to image fracture zones in crystalline rock are presented. Two examples using reflection seismic are presented. The first is from the 5354 m deep SG-4 borehole in the Middle Urals, Russia where strong seismic reflectors dipping from 25 to 50 degrees are observed on surface seismic reflection data crossing over the borehole. On vertical seismic profile data acquired in the borehole, the observed P-wave reflectivity is weak from these zones, however, strong converted P to S waves are observed. This can be explained by the source of the reflectors being fracture zones with a high P wave to S wave velocity ratio compared to the surrounding rock resulting in a high dependence on the angle of incidence for the reflection coefficient. A high P wave to S wave velocity ratio (high Poisson's ratio) is to be expected in fluid filled fractured rock. The second case is from Aevroe, SE Sweden, where two 1 km long crossing high resolution seismic reflection lines were acquired in October 1996. An E-W line was shot with 5 m geophone and shotpoint spacing and a N-S one with 10 m geophone and shotpoint spacing. An explosive source with a charge size of 100 grams was used along both lines. The data clearly image three major dipping reflectors in the upper 200 ms (600 m). The dipping ones intersect or project to the surface at/or close to

  20. Optimization of Remediation Conditions using Vadose Zone Monitoring Technology

    Science.gov (United States)

    Dahan, O.; Mandelbaum, R.; Ronen, Z.

    2010-12-01

    Success of in-situ bio-remediation of the vadose zone depends mainly on the ability to change and control hydrological, physical and chemical conditions of subsurface. These manipulations enables the development of specific, indigenous, pollutants degrading bacteria or set the environmental conditions for seeded bacteria. As such, the remediation efficiency is dependent on the ability to implement optimal hydraulic and chemical conditions in deep sections of the vadose zone. Enhanced bioremediation of the vadose zone is achieved under field conditions through infiltration of water enriched with chemical additives. Yet, water percolation and solute transport in unsaturated conditions is a complex process and application of water with specific chemical conditions near land surface dose not necessarily result in promoting of desired chemical and hydraulic conditions in deeper sections of the vadose zone. A newly developed vadose-zone monitoring system (VMS) allows continuous monitoring of the hydrological and chemical properties of the percolating water along deep sections of the vadose zone. Implementation of the VMS at sites that undergoes active remediation provides real time information on the chemical and hydrological conditions in the vadose zone as the remediation process progresses. Manipulating subsurface conditions for optimal biodegradation of hydrocarbons is demonstrated through enhanced bio-remediation of the vadose zone at a site that has been contaminated with gasoline products in Tel Aviv. The vadose zone at the site is composed of 6 m clay layer overlying a sandy formation extending to the water table at depth of 20 m bls. The upper 5 m of contaminated soil were removed for ex-situ treatment, and the remaining 15 m vadose zone is treated in-situ through enhanced bioremedaition. Underground drip irrigation system was installed below the surface on the bottom of the excavation. Oxygen and nutrients releasing powder (EHCO, Adventus) was spread below the