Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

International audienc

Kinetics and Mechanism of the Reaction of Cl Atoms with HO 2 Radicals

ABSTRACT: The kinetics and mechanism of the reaction Cl ϩ HO 2 : products (1) have been studied in the temperature range 230-360 K and at total pressure of 1 Torr of helium using the discharge-flow mass spectrometric method. The following Arrhenius expression for the total rate constant was obtained either from the kinetics of HO 2 consumption in excess of Cl atoms or from the kinetics of Cl in excess of HO 2 : , where uncertainties are 95% confidence limits. The temperature-independent value of k 1 ϭ (4.4 Ϯ 0.6) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 at T ϭ 230-360 K, which can be recommended from this study, agrees well with most recent studies and current recommendations. Both OH and ClO were detected as the products of reaction (1) and the rate constant for the channel forming these species, Cl ϩ HO 2 : OH ϩ ClO (1b), has been determined: k 1b ϭ (8.6 Ϯ 3.2) ϫ 10 Ϫ11 exp[Ϫ(660 Ϯ 100)/T] cm 3 molecule Ϫ1 s Ϫ1 (with k 1b ϭ (9.4 Ϯ 1.9) ϫ 10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 at T ϭ 298 K), where uncertainties represent 95% confidence limits

Crystalline silicate dust around evolved stars I. The sample stars

This is the first paper in a series of three where we present the first comprehensive inventory of solid state emission bands observed in a sample of 17 oxygen-rich circumstellar dust shells surrounding evolved stars. The data were taken with the Short and Long Wavelength Spectrographs on board of the Infrared Space Observatory (ISO) and cover the 2.4 to 195 micron wavelength range. The spectra show the presence of broad 10 and 18 micron bands that can be attributed to amorphous silicates. In addition, at least 49 narrow bands are found whose position and width indicate they can be attributed to crystalline silicates. Almost all of these bands were not known before ISO. We have measured the peak positions, widths and strengths of the individual, continuum subtracted bands. Based on these measurements, we were able to order the spectra in sequence of decreasing crystalline silicate band strength. We found that the strength of the emission bands correlates with the geometry of the circumstellar shell, as derived from direct imaging or inferred from the shape of the spectral energy distribution. This naturally divides the sample into objects that show a disk-like geometry (strong crystalline silicate bands), and objects whose dust shell is characteristic of an outflow (weak crystalline silicate bands). All stars with the 33.6 micron forsterite band stronger than 20 percent over continuum are disk sources. We define spectral regions (called complexes) where a concentration of emission bands is evident, at 10, 18, 23, 28, 33, 40 and 60 micron. We derive average shapes for these complexes and compare these to the individual band shapes of the programme stars.Comment: 41 pages, 20 figures, accepted by A&A. Tables 4 to 20 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A

Local and regional components of aerosol in a heavily trafficked street canyon in central London derived from PMF and cluster analysis of single-particle ATOFMS spectra.

Positive matrix factorization (PMF) has been applied to single particle ATOFMS spectra collected on a six lane heavily trafficked road in central London (Marylebone Road), which well represents an urban street canyon. PMF analysis successfully extracted 11 factors from mass spectra of about 700,000 particles as a complement to information on particle types (from K-means cluster analysis). The factors were associated with specific sources and represent the contribution of different traffic related components (i.e., lubricating oils, fresh elemental carbon, organonitrogen and aromatic compounds), secondary aerosol locally produced (i.e., nitrate, oxidized organic aerosol and oxidized organonitrogen compounds), urban background together with regional transport (aged elemental carbon and ammonium) and fresh sea spray. An important result from this study is the evidence that rapid chemical processes occur in the street canyon with production of secondary particles from road traffic emissions. These locally generated particles, together with aging processes, dramatically affected aerosol composition producing internally mixed particles. These processes may become important with stagnant air conditions and in countries where gasoline vehicles are predominant and need to be considered when quantifying the impact of traffic emissions.This is the author accepted manuscript. The final version is available via ACS at http://pubs.acs.org/doi/abs/10.1021/es506249z

Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons – a review

Polycyclic aromatic hydrocarbons (PAHs) are of considerable concern due to their well-recognised toxicity and especially due to the carcinogenic hazard which they present. PAHs are semi-volatile and therefore partition between vapour and condensed phases in the atmosphere and both the vapour and particulate forms undergo chemical reactions. This article briefly reviews the current understanding of vapour-particle partitioning of PAHs and the PAH deposition processes, and in greater detail, their chemical reactions. PAHs are reactive towards a number of atmospheric oxidants, most notably the hydroxyl radical, ozone, the nitrate radical (NO3) and nitrogen dioxide. Rate coefficient data are reviewed for reactions of lower molecular weight PAH vapour with these species as well as for heterogeneous reactions of higher molecular weight compounds. Whereas the data for reactions of the 2-3-ring PAH vapour are quite extensive and generally consistent, such data are mostly lacking for the 4-ring PAHs and the heterogeneous rate data (5 and more rings), which are dependent on the substrate type and reaction conditions, are less comprehensive. The atmospheric reactions of PAH lead to the formation of oxy and nitro derivatives, reviewed here, too. Finally, the capacity of PAHs for long range transport and the results of numerical model studies are described. Research needs are identified