Detrital-zircon geochronology and provenance of the Ocloyic synorogenic clastic wedge, and Ordovician accretion of the Argentine Precordillera terrane

The Precordillera terrane in northwestern Argentina is interpreted to be anexotic (Laurentian) continental fragment that was accreted to western Gondwanaduring the Ordovician. One prominent manifestation of the subductionand collision process is a Middle?Upper Ordovician clastic wedge, which overliesa passive-margin carbonate-platform succession in the Precordillera. U/Pbages of detrital zircons from sandstones within the clastic wedge, as well as zirconsfrom clasts within conglomerates, provide documentation for the compositionof the sediment provenance. The ages of detrital zircons are consistentvertically through the succession, as well as laterally along and across strike ofthe Precordillera, indicating a single, persistent sediment source throughoutdeposition of the clastic wedge. The dominant mode (~1350?1000 Ma) of thedetrital-zircon ages corresponds to the ages of basement rocks in the WesternSierras Pampeanas along the eastern side of the Precordillera. A secondarymode (1500?1350 Ma) corresponds in age to the Granite-Rhyolite province ofLaurentia, an age range which is not known in ages of basement rocks of theWestern Sierras Pampeanas; however, detritus from Granite-Rhyolite-age rocksin the basement of the Precordillera was available through recycling of synriftand passive-margin cover strata. Igneous clasts in the conglomerates haveages (647?614 Ma) that correspond to the ages of minor synrift igneous rocks inthe nearby basement massifs; the same ages are represented in a minor mode(~750?570 Ma) of detrital-zircon ages. A quartzite clast in a conglomerate, aswell as parts of the population of detrital zircons, indicates the importanceof a source in the metasedimentary cover of the leading edge of the Precordillera.The Famatina continental-margin magmatic arc reflects pre-collisionsubduction of Precordillera lithosphere beneath the western Gondwana margin;however, no detrital zircons have ages that correspond to Famatina arcmagmatism, indicating that sedimentary detritus from the arc may have beentrapped in a forearc basin and did not reach the foreland. The indicators ofsedimentary provenance for the foreland deposits are consistent with subductionof the Precordillera beneath western Gondwana, imbrication of basementrocks from either the Precordillera or Gondwana into an accretionary complex,and recycling of deformed Precordillera cover rocks.Fil: Thomas, William A.. Geological Survey of Alabama; Estados UnidosFil: Astini, Ricardo Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Mueller, Paul A.. Florida State University; Estados UnidosFil: McClelland, William C.. University of Iowa; Estados Unido

Development and Validation of ReaxFF Reactive Force Field for Hydrocarbon Chemistry Catalyzed by Nickel

To enable the study of hydrocarbon reactions catalyzed by nickel surfaces and particles using reactive molecular dynamics on thousands of atoms as a function of temperature and pressure, we have developed the ReaxFF reactive force field to describe adsorption, decomposition, reformation and desorption of hydrocarbons as they interact with the nickel surface. The ReaxFF parameters were determined by fitting to the geometries and energy surfaces from quantum mechanics (QM) calculations for a large number of reaction pathways for hydrocarbon molecules chemisorbed onto nickel (111), (100) and (110) surfaces, supplemented with QM equations of state for nickel and nickel carbides. We demonstrate the validity and accuracy of ReaxFF by applying it to study the reaction dynamics of hydrocarbons as catalyzed by nickel particles and surfaces. For the dissociation of methyl on the (111), (100), and stepped (111) surfaces of nickel, we observe the formation of chemisorbed CH plus subsurface carbide. We observe that the (111) surface is the least reactive, the (100) surface has the fastest reaction rates, and the stepped (111) surface has an intermediate reaction rate. The importance of surface defects in accelerating reaction rates is highlighted by these results

Structures, Energetics, and Reaction Barriers for CH_x Bound to the Nickel (111) Surface

To provide a basis for understanding and improving such reactive processes on nickel surfaces as the catalytic steam reforming of hydrocarbons, the decomposition of hydrocarbons at fuel cell anodes, and the growth of carbon nanotubes, we report quantum mechanics calculations (PBE flavor of density functional theory, DFT) of the structures, binding energies, and reaction barriers for all CH_x species on the Ni(111) surface using periodically infinite slabs. We find that all CH_x species prefer binding to μ3 (3-fold) sites leading to bond energies ranging from 42.7 kcal/mol for CH_3 to 148.9 kcal/mol for CH (the number of Ni-C bonds is not well-defined). We find reaction barriers of 18.3 kcal/mol for CH_(3,ad) → CH_(2,ad) + H_(ad) (with ΔE = +1.3 kcal/ mol), 8.2 kcal/mol for CH_(2,ad) → CH_(ad) + H_(ad) (with ΔE = -10.2 kcal/mol) and 32.3 kcal/mol for CH_(ad) → C_(ad) + H_(ad) (with ΔE = 11.6 kcal/mol). Thus, CH_(ad) is the stable form of CH_x on the surface. These results are in good agreement with the experimental data for the thermodynamic stability of small hydrocarbon species following dissociation of methane on Ni(111) and with the intermediates isolated during the reverse methanation process

Competing, Coverage-Dependent Decomposition Pathways for C_2H_y Species on Nickel (111)

Competing, coverage-dependent pathways for ethane (CH_3CH_3) decomposition on Ni(111) are proposed on the basis of quantum mechanics (QM) calculations, performed by using the PBE flavor of density functional theory (DFT), for all C_2H_y species adsorbed to a periodically infinite Ni(111) surface. For CH_2CH_3, CHCH_3, and CCH_3, we find that the surface C is tetrahedral in each case, with the surface C forming bonds to one, two, or three Ni atoms with bond energies scaling nearly linearly (E_(bond) = 32.5, 82.7, and 130.8 kcal/mol, respectively). In each of the remaining six C_2H_y species, both C atoms are able to form bonds to the surface. Three of these (CH_2CH_2, CHCH_2, and CCH_2) adsorb most favorably at a fcc-top site with the methylene C located at an on-top site and the other C at an adjacent fcc site. The bond energies for these species are E_(bond) = 19.7, 63.2, and 93.6 kcal/mol, respectively. The remaining species (CHCH, CCH, and C_2) all prefer binding at fcc-hcp sites, where the C atoms sit in a pair of adjacent fcc and hcp sites, with binding energies of E_(bond) = 57.7, 120.4, and 162.8 kcal/mol, respectively. We find that CHCH_(ad) is the most stable surface species (ΔH_(eth) = −18.6), and an important intermediate along the lowest-energy decomposition pathway for ethane on Ni(111). The second most stable species, CCH_3, is a close competitor (ΔH_(eth) = −18.2 kcal/mol), lying along an alternative decomposition pathway that is preferred for high-surface-coverage conditions. The existence of these competing, low- and high-coverage decomposition pathways is consistent with the experiments. The QM results reported here were used as training data in the development of the ReaxFF reactive force field describing hydrocarbon reactions on nickel surfaces [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 4939−4949]. This has enabled Reactive dynamics studying the chemisorption and decomposition of systems far too complex for quantum mechanics. Thus we reported recently, the chemisorption and decomposition of six different hydrocarbon species on a Ni_(468) nanoparticle catalysts using this ReaxFF description [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 5675−5685]

Sewage sludge treatment system

Raw sewage may be presently treated by mixing screened raw sewage with activated carbon. The mixture is then allowed to stand in a first tank for a period required to settle the suspended matter to the bottom of the tank as a sludge. Thereafter, the remaining liquid is again mixed with activated carbon and the mixture is transferred to a secondary settling tank, where it is permitted to stand for a period required for the remaining floating material to settle as sludge and for adsorption of sewage carbon as well as other impurities to take place. The sludge from the bottom of both tanks is removed and pyrolyzed to form activated carbon and ash, which is mixed with the incoming raw sewage and also mixed with the liquid being transferred from the primary to the secondary settling tank. It has been found that the output obtained by the pyrolysis process contains an excess amount of ash. Removal of this excess amount of ash usually also results in removing an excess amount of carbon thereby requiring adding carbon to maintain the treatment process. By separately pyrolyzing the respective sludges from the first and second settling tanks, and returning the separately obtained pyrolyzed material to the respective first and second tanks from which they came, it has been found that the adverse effects of the excessive ash buildup is minimized, the carbon yield is increased, and the sludge from the secondary tank can be pyrolyzed into activated carbon to be used as indicated many more times than was done before exhaustion occurs

The ultraviolet absorption spectra of some substituted acetophenones

In order to investigate more fully the steric influences in the B-band of the ultraviolet spectrum, several acetophenones were prepared, giving molecules in which the angle between the planes of the electron rich centers varied. It was found that the light absorption maximum moved to shorter wavelengths as the amount of hindrance about the carbonyl group was increased, (i.e., as the interplanar angle was increased), and that steric hindrance increased in the order hydrogen atom <. ortho-methylene group of the cyclopentyl ring ( ortho-methyl group z orthomethylene group of tbe cyclohexyl ring ( an orthomethyl group ''buttressed'' by a methyl group in the adjacent meta-position. The carbonyl group becomes less readily accessible as steric interference is increased, as shown by the inability of the highly hindered ketones to form the ordinary ketone derivatives. In the highly hindered ketones, conjugation is inhibited to such an extent that the main peaks closely correspond to those of the substituted benzenoid hydrocarbons. The spatial orientation of the compounds is discussed by interpreting the spectra in terms of the electronic and steric effects of the substituents. The 2,4-dinitrophenylhydrazones of the unsubstituted compounds, and some of the substituted aompounds are included, and it was found that the amount of steric hindrance c,an sometimes be estimated by color, 1.e., as conjugation increases, the colors tend from yellow to red. A recent example from the literature on the spectra of substituted hydroxybenzoic acids is included, and it was found possible to correlate nicely the observed spectra by means of the theories of ster.ic and el1ectronic effects. In the experimental part, the syntheses of the ketones are described, along with the reaction of β-chloropropionyl chloride with tetralin, and an attempt to prepare 2,3,5,6-tetraethylbenzene

Coating for gasifiable carbon-graphite fibers

A thin, uniform, firmly adherent coating of metal gasification catalyst is applied to a carbon-graphite fiber by first coating the fiber with a film-forming polymer containing functional moieties capable of reaction with the catalytic metal ions. Multivalent metal cations such as calcium cross-link the polymer such as a polyacrylic acid to insolubilize the film by forming catalytic metal macro-salt links between adjacent polymer chains. The coated fibers are used as reinforcement for resin composites and will gasify upon combustion without evolving conductive airborne fragments