On the relevance of the methane oxidation cycle to ozone hole chemistry

High concentrations of active chlorine are clearly responsible for the observed ozone depletion during the Antarctic polar spring. However, the mechanism behind the activation of chlorine from the reservoirs species HCl and ClONO2 and the maintenance of extremely high levels of active chlorine after polar sunrise is less well understood. Here, we focus on the influence of the methane oxidation cycle on 'ozone hole' chemistry through its effect on HOx and ClOx radicals. We demonstrate the great potential importance of the heterogeneous reaction HCl + HOCl yields Cl2 + H2O and the gasphase reaction ClO + CH3O2 yields ClOO + CH3O under sunlight conditions in polar spring. Under these conditions, the heterogeneous reaction is the main sink for HOx radicals. Through this channel, the HCl reservoir may be almost completely depleted. The gas phase reaction may control the levels of the CH3O2 radical, provided that high levels of ClO exist. Otherwise this radical initiates a sequence of reactions leading to a considerable loss of active chlorine. Moreover, the production of HOx radicals is reduced, and thereby the efficiency of the heterogeneous reaction limited. The two reactions together may accomplish the complete conversion of HCl into active chlorine, thereby leading to a rapid destruction of ozone

Estimates of the changes in tropospheric chemistry which result from human activity and their dependence on NO(x) emissions and model resolution

As a consequence of the non-linear behavior of the chemistry of the atmosphere and because of the short lifetime of nitrogen oxides (NO(x)), two-dimensional models do not give an adequate description of the production and destruction rates of NO(x) and their effects on the distributions of the concentration of ozone and hydroxyl radical. In this study, we use a three-dimensional model to evaluate the contribution of increasing NO(x) emissions from industrial activity and biomass burning to changes in the chemical composition of the troposphere. By comparing results obtained from longitudinally-uniform and longitudinally-varying emissions of NO(x), we demonstrate that the geographical representation of the NO(x) emissions is crucial in simulating tropospheric chemistry

Temperature dependence of UV absorption cross sections and atmospheric implications of several alkyl iodides

The ultraviolet absorption spectra of a number of alkyl iodides which have been found in the troposphere, CH_3I, C_2H_5I, CH_3CH_2CH_2I, CH_3CHICH_3, CH_2I_2, and CH2_ClI, have been measured over the wavelength range 200–380 nm and at temperatures between 298 and 210 K. The absorption spectra of the monoiodides C_H3I, C_2H_5I, CH_3CH_2CH_2I, and CH_3CHICH_3 are nearly identical in shape and magnitude and consist of single broad bands centered near 260 nm. The addition of a chlorine atom in CH_2ClI shifts its spectrum to longer wavelengths (σ_(max) at 270 nm). The spectrum of CH_2I_2 is further red‐shifted, reaching a maximum of 3.85×10^(−18) cm^2 molecule^(−1) at 288 nm and exhibiting strong absorption in the solar actinic region, λ>290 nm. Atmospheric photolysis rate constants, J values, have been calculated assuming quantum efficiencies of unity for different solar zenith angles as a function of altitude using the newly measured cross sections. Surface photolysis rate constants, calculated from the absorption cross sections measured at 298 K, range from 3×10^(−6) s^(−1) for CH)3I to 5×10^(−3) s^(−1) for CH)2I)2 at a solar zenith angle of 40°

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

Biomass burning emission inventory with daily resolution: Application to aircraft observations of Asian outflow

Asian outflo

Temperature dependence of UV absorption cross sections and atmospheric implications of several alkyl iodides

The ultraviolet absorption spectra of a number of alkyl iodides which have been found in the troposphere, CH_3I, C_2H_5I, CH_3CH_2CH_2I, CH_3CHICH_3, CH_2I_2, and CH2_ClI, have been measured over the wavelength range 200–380 nm and at temperatures between 298 and 210 K. The absorption spectra of the monoiodides C_H3I, C_2H_5I, CH_3CH_2CH_2I, and CH_3CHICH_3 are nearly identical in shape and magnitude and consist of single broad bands centered near 260 nm. The addition of a chlorine atom in CH_2ClI shifts its spectrum to longer wavelengths (σ_(max) at 270 nm). The spectrum of CH_2I_2 is further red‐shifted, reaching a maximum of 3.85×10^(−18) cm^2 molecule^(−1) at 288 nm and exhibiting strong absorption in the solar actinic region, λ>290 nm. Atmospheric photolysis rate constants, J values, have been calculated assuming quantum efficiencies of unity for different solar zenith angles as a function of altitude using the newly measured cross sections. Surface photolysis rate constants, calculated from the absorption cross sections measured at 298 K, range from 3×10^(−6) s^(−1) for CH)3I to 5×10^(−3) s^(−1) for CH)2I)2 at a solar zenith angle of 40°

Haloe Antarctic observations in the spring of 1991

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95167/1/grl6630.pd

Gravitational Radiation from Gamma-Ray Burst Progenitors

We study gravitational radiation from various proposed gamma-ray burst (GRB) progenitor models, in particular compact mergers and massive stellar collapses. These models have in common a high angular rotation rate, and the final stage involves a rotating black hole and accretion disk system. We consider the in-spiral, merger and ringing phases, and for massive collapses we consider the possible effects of asymmetric collapse and break-up, as well bar-mode instabilities in the disks. We calculate the strain and frequency of the gravitational waves expected from various progenitors, at distances based on occurrence rate estimates. Based on simplifying assumptions, we give estimates of the probability of detection of gravitational waves by the advanced LIGO system from the different GRB scenarios.Comment: 26 pages, 5 figures, accepted for publication in Ap

Differential modes of DNA binding by mismatch uracil DNA glycosylase from Escherichia coli: implications for abasic lesion processing and enzyme communication in the base excision repair pathway

Mismatch uracil DNA glycosylase (Mug) from Escherichia coli is an initiating enzyme in the base-excision repair pathway. As with other DNA glycosylases, the abasic product is potentially more harmful than the initial lesion. Since Mug is known to bind its product tightly, inhibiting enzyme turnover, understanding how Mug binds DNA is of significance when considering how Mug interacts with downstream enzymes in the base-excision repair pathway. We have demonstrated differential binding modes of Mug between its substrate and abasic DNA product using both band shift and fluorescence anisotropy assays. Mug binds its product cooperatively, and a stoichiometric analysis of DNA binding, catalytic activity and salt-dependence indicates that dimer formation is of functional significance in both catalytic activity and product binding. This is the first report of cooperativity in the uracil DNA glycosylase superfamily of enzymes, and forms the basis of product inhibition in Mug. It therefore provides a new perspective on abasic site protection and the findings are discussed in the context of downstream lesion processing and enzyme communication in the base excision repair pathway