1,401 research outputs found

    Ethnic differences in fetal growth, birth weight and infant mortality: The Generation R Study

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    Antilliaanse kinderen in Nederland hebben vijftig procent meer kans om te overlijden in het eerste levensjaar dan autochtone kinderen. Dit blijkt uit onderzoek van Ernst-Jan Troe van het Erasmus MC. Het verhoogde risico komt vooral door een lager geboortegewicht en kortere zwangerschapsduur. Mogelijke risicofactoren zijn dat Antilliaanse zwangere vrouwen vaker alleenstaand of tiener zijn

    Shock wave study and theoretical modeling of the thermal decomposition of c-C4F8

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    The thermal dissociation of octafluorocyclobutane, c-C4F8, was studied in shock waves over the range 1150-2300 K by recording UV absorption signals of CF2. It was found that the primary reaction nearly exclusively produces 2 C2F4 which afterwards decomposes to 4 CF2. A primary reaction leading to CF2 + C3F6 is not detected (an upper limit to the yield of the latter channel was found to be about 10 percent). The temperature range of earlier single pulse shock wave experiments was extended. The reaction was shown to be close to its high pressure limit. Combining high and low temperature results leads to a rate constant for the primary dissociation of k1 = 1015.97 exp(-310.5 kJ mol-1/RT) s-1 in the range 630-1330 K, over which k1 varies over nearly 14 orders of magnitude. Calculations of the energetics of the reaction pathway and the rate constants support the conclusions from the experiments. Also they shed light on the role of the 1,4-biradical CF2CF2CF2CF2 as an intermediate of the reaction.Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Hintzer, K.. Dyneon Gmbh; AlemaniaFil: Sölter, L.. Universität Göttingen; AlemaniaFil: Tellbach, E.. Universität Göttingen; AlemaniaFil: Thaler, A.. Dyneon Gmbh; AlemaniaFil: Troe, J.. Universität Göttingen; Alemania. Max-Planck-Institut fu¨r biophysikalische Chemie; Alemani

    Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

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    We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalysed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.Comment: Accepted for publication in Space Science Review

    Excitation and abundance study of CO+ in the interstellar medium

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    Observations of CO+ suggest column densities on the order 10^12 cm^-2 that can not be reproduced by many chemical models. CO+ is more likely to be destroyed than excited in collisions with hydrogen. An anomalous excitation mechanism may thus have to be considered when interpreting CO^+ observations. Chemical models are used to perform a parameter study of CO^+ abundances. Line fluxes are calculated for N(CO+)=10^12 cm^-2 and different gas densities and temperatures using a non-LTE escape probability method. The chemical formation and destruction rates are considered explicitly in the detailed balance equations of the radiative transfer. In addition, the rotational levels of CO+ are assumed to be excited upon chemical formation according to a formation temperature. It is found, that chemical models are generally able to produce high fractional CO+ abundances (x(CO+) =10^-10). In a far-ultraviolet (FUV) dominated environment, however, high abundances of CO+ are only produced in regions with a Habing field G0 > 100 and T(kin) > 600 K, posing a strong constraint on the gas temperature. For gas densities >10^6 cm^-3 and temperatures > 600 K, the combination of chemical and radiative transfer analysis shows little effect on intensities of CO+ lines with upper levels N_up <= 3. Significantly different line fluxes are calculated with an anomalous excitation mechanism, however, for transitions with higher upper levels and densities >10^6 cm ^ -3. The Herschel Space Observatory is able to reveal such effects in the terahertz wavelength regime. Ideal objects to observe are protoplanetary disks with densities 10^6 cm^-3. It is finally suggested that the CO+ chemistry may be well understood and that the abundances observed so far can be explained with a high enough gas temperature and a proper geometry.Comment: 9 pages, 7 figure

    Water formation at low temperatures by surface O2 hydrogenation I: characterization of ice penetration

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    Water is the main component of interstellar ice mantles, is abundant in the solar system and is a crucial ingredient for life. The formation of this molecule in the interstellar medium cannot be explained by gas-phase chemistry only and its surface hydrogenation formation routes at low temperatures (O, O2, O3 channels) are still unclear and most likely incomplete. In a previous paper we discussed an unexpected zeroth-order H2O production behavior in O2 ice hydrogenation experiments compared to the first-order H2CO and CH3OH production behavior found in former studies on hydrogenation of CO ice. In this paper we experimentally investigate in detail how the structure of O2 ice leads to this rare behavior in reaction order and production yield. In our experiments H atoms are added to a thick O2 ice under fully controlled conditions, while the changes are followed by means of reflection absorption infrared spectroscopy (RAIRS). The H-atom penetration mechanism is systematically studied by varying the temperature, thickness and structure of the O2 ice. We conclude that the competition between reaction and diffusion of the H atoms into the O2 ice explains the unexpected H2O and H2O2 formation behavior. In addition, we show that the proposed O2 hydrogenation scheme is incomplete, suggesting that additional surface reactions should be considered. Indeed, the detection of newly formed O3 in the ice upon H-atom exposure proves that the O2 channel is not an isolated route. Furthermore, the addition of H2 molecules is found not to have a measurable effect on the O2 reaction channel.Comment: 1 page, 1 figur

    Rich methane laminar flames doped with light unsaturated hydrocarbons. Part II: 1,3butadiene

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    In line with the study presented in the part I of this paper, the structure of a laminar rich premixed methane flame doped with 1,3-butadiene has been investigated. The flame contains 20.7% (molar) of methane, 31.4% of oxygen and 3.3% of 1,3-butadiene, corresponding to an equivalence ratio of 1.8, and a ratio C4H6 / CH4 of 16 %. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The temperature ranged from 600 K close to the burner up to 2150 K. Quantified species included usual methane C0-C2 combustion products and 1,3-butadiene, but also propyne, allene, propene, propane, 1,2-butadiene, butynes, vinylacetylene, diacetylene, 1,3-pentadiene, 2-methyl-1,3-butadiene (isoprene), 1-pentene, 3-methyl-1-butene, benzene and toluene. In order to model these new results, some improvements have been made to a mechanism previously developed in our laboratory for the reactions of C3-C4 unsaturated hydrocarbons. The main reaction pathways of consumption of 1,3-butadiene and of formation of C6 aromatic species have been derived from flow rate analyses. In this case, the C4 route to benzene formation plays an important role in comparison to the C3 pathway

    Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates

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    This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made

    A Comparative Study of the Formation of Aromatics in Rich Methane Flames Doped by Unsaturated Compounds

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    For a better modeling of the importance of the different channels leading to the first aromatic ring, we have compared the structures of laminar rich premixed methane flames doped with several unsaturated hydrocarbons: allene and propyne, because they are precursors of propargyl radicals which are well known as having an important role in forming benzene, 1,3-butadiene to put in evidence a possible production of benzene due to reactions of C4 compounds, and, finally, cyclopentene which is a source of cyclopentadienylmethylene radicals which in turn are expected to easily isomerizes to give benzene. These flames have been stabilized on a burner at a pressure of 6.7 kPa (50 Torr) using argon as dilutant, for equivalence ratios (?) from 1.55 to 1.79. A unique mechanism, including the formation and decomposition of benzene and toluene, has been used to model the oxidation of allene, propyne, 1,3 butadiene and cyclopentene. The main reaction pathways of aromatics formation have been derived from reaction rate and sensitivity analyses and have been compared for the three types of additives. These combined analyses and comparisons can only been performed when a unique mechanism is available for all the studied additives

    Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II ? gas phase reactions of organic species

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    International audienceThis article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made

    Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II ? reactions of organic species

    No full text
    International audienceThis article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made
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