Kinetics of the Reaction of Hydroxyl Radicals with CH2Br2 and its Implications in the Atmosphere

Rate constants for the reaction of hydroxyl radicals with dibromomethanehave been measured by discharge flow-resonance fluorescence technique(DF-RF) over the temperature range 288–368 K. The derived Arrheniusequation is k₁=(1.51 ± 0.37)× 10^-12 exp(-(720 ±60)/T) cm³ molec.^-1 s^-1.The tropospheric lifetime of dibromomethane has been estimated to be 0.29years. An ozone depletion potential (ODP) value of 0.10 for dibromomethanehas been obtained.     

Aerosol Indirect Effects on Warm Clouds in the Grid-Point Atmospheric Model of IAP LASG (GAMIL)

Aerosol indirect effects on warm clouds are estimated in the Grid-point Atmospheric Model of the State Key Laboratory of Numerical Modeling for Atmospheric Sciences and Geophysical Fluid Dynamics,Institute of Atmospheric Physics(IAP LASG)(GAMIL) with a new two-moment cloud microphysics scheme using two different physically-based aerosol activation parameterizations:Abdul-Razzak and Ghan,and Nenes and Seinfeld.The annual global mean changes in shortwave cloud forcing from preindustrial times to present day(a measure of the aerosol indirect effects) estimated from these two parameterizations are remarkably similar:0.76 W m?2 with the Abdul-Razzak and Ghan parameterization,and 0.78 W m?2 with the Nenes and Seinfeld parameterization.Physically-based parameterizations can provide robust representations of aerosol effects on droplet nucleation,meaning that aerosol activation is no longer the most uncertain factor in modeling aerosol indirect effects.     

SEM-EDX Characterisation of Tropospheric Aerosols in the Negev Desert (Israel)

Individual aerosol particles collected in the Negev desert in Israel during a summer and winter campaign in 1996–1997 were analysed by scanning electron microscopy with energy-dispersive X-ray analysis. Hierarchical cluster analysis was performed to interpret the data on the basis of particle diameter and composition. Eleven particle classes (groups) provided clues on sources and/or particle formation. The summer samples were enriched in sulphates and mineral dusts; the winter samples contained more sea salts, aged sea salts, and industrial particles. The fine size fraction below 1 m diameter was enriched in secondary particles and showed evidence of atmospheric processing. The secondary sulphate particles were mainly attributed to long-range transport. A regional conversion from calcite to calcium sulphate occurred during summer. Industrial particles originating from local pollution appeared during winter.     

Direct Climatic Effect of Dust Aerosol in the NCAR Community Atmosphere Model Version 3 （CAM3）

Direct climate responses to dust shortwave and longwave radiative forcing (RF) are studied using the NCAR Community Atmosphere Model Version 3 (CAM3). The simulated RF at the top of the atmosphere (TOA) is-0.45 W m-2 in the solar spectrum and +0.09 W m-2 in the thermal spectrum on a global average. The magnitude of surface RF is larger than the TOA forcing, with global mean shortwave forcing of-1.76 W m-2 and longwave forcing of +0.31 W m-2 . As a result, dust aerosol causes the absorption of 1.1 W m-2 in t...     

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.     

The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D _ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O₂-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]     

Secular evolution of the vertical column abundances of CHCIF2 (HCFC-22) in the Earth's atmosphere inferred from ground-based IR solar observations at the Jungfraujoch and at Kitt Peak,and comparison with model calculations

Series of high-resolution infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, between 06/1986 and 11/1992, and at Kitt Peak National Observatory, Tucson, Arizona (U.S.A.), from 12/1980 to 04/1992, have been analyzed to provide a comprehensive ensemble of vertical column abundances of CHCIF₂ (HCFC-22; Freon-22) above the European and the North American continents. The columns were derived from nonlinear least-squares curve fittings between synthetic spectra and the observations containing the unresolved 2v ₆ Q-branch absorption of CHCIF₂ at 829.05 cm^–1. The changes versus time observed in these columns were modeled assuming both an exponential and a linear increase with time. The exponential rates of increase at one-sigma uncertainties were found equal to (7.0±0.35)%/yr for the Junfraujoch data and (7.0±0.23)%/yr for the Kitt Peak data. The exponential trend of 7.0%/yr found at both stations widely separated in location can be considered as representative of the global increase of the CHCIF₂ burden in the Earth's atmosphere during the period 1980 to 1992. When assuming two realistic vertical volume mixing ratio profiles for CHCIF₂ in the troposphere, one quasi constant and the other decreasing by about 13% from the ground to the tropopause, the concentrations for mid-1990 were found to lie between 97 and 111 pptv (parts per trillion by volume) at the 3.58 km altitude of the Jungfraujoch and between 97 and 103 pptv at Kitt Peak, 2.09 km above sea level. Corresponding values derived from calculations using a high vertical resolution-2D model and recently compiled HCFC-22 releases to the atmosphere, were equal to 107 and 105 pptv, respectively, in excellent agreement with the measurements. The model calculated lifetime of CHCIF₂ was found equal to 15.6 years. The present results are compared critically with similar data found in the literature. On average, the concentrations found here are lower by 15–20% than those derived from in situ investigations; this difference cannot be explained by the absolute uncertainty of ±11% assigned presently to the infrared remote measurements.