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We present measurements of stratospheric aerosol made at Aberystwyth, UK (52.4° N, 4.06° W) during periods of background aerosol conditions. The measurements were made with a lidar system based on a 532nm laser and two polarisation channels in the receiver. When stratospheric aerosol amounts are very small, as at present, this method is, potentially, free of a number of systematic errors that bedevil more commonly-used methods. The method rests on the assumption that the aerosol consists of spherical droplets which do not depolarise the lidar signal, which is valid under most conditions. Maximum lidar ratios in background aerosol of 1.03-1.06 were measured during the period 2001-2004, with integrated backscatter in the range 2-7x10<sup>-5</sup>sr<sup>-1</sup>. In January 2003, depolarising aerosol was measured, which invalidated the dual-polarisation measurements. On 10-11 January, the depolarising aerosol was clearly a polar stratospheric cloud (the first lidar observations of such clouds in the British Isles) but the aerosol observed on 7-8 January was too low in altitude and too warm to be a PSC.
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Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a one dimensional model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion) and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently "recycles" less reactive bromine species (e.g. HBr) and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.
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Scattering and absorption coefficients have been measured continuously at several wavelengths since March 2001 at the high altitude site Jungfraujoch (3580ma.s.l.). From these data, the wavelength dependences of the Ångström exponent and particularly of the single scattering albedo are determined. While the exponent of the single scattering albedo usually increases with wavelength, it decreases with wavelength during Saharan dust events (SDE) due to the greater size of the mineral aerosol particles and their different chemical composition. This change in the sign of the single scattering exponent turns out to be a sensitive means for detecting Saharan dust events. The occurrence of SDE detected by this new method was confirmed by visual inspection of filter colors and by studying long-range back-trajectories. An examination of SDE over a 22-month period shows that SDE are more frequent during the March-June period as well as during October and November. The trajectory analysis indicated a mean traveling time of 96.5h, with the most important source countries situated in the northern and north-western part of the Saharan desert. Most of the SDE do not lead to a detectable increase of the 48-h total suspended particulate matter (TSP) concentration at the Jungfraujoch. During Saharan dust events, the average contribution of this dust to hourly TSP at the Jungfraujoch is 16µg/m<sup>3</sup>, which corresponds to an annual mean of 0.8µg/m<sup>3</sup> or 24% of TSP.
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Recently several field campaigns and satellite observations have found strong indications for the presence of bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO mixing ratios of a few tenths to 2 pmol mol<sup>-1</sup> lead to a reduction in the zonal mean O<sub>3</sub> mixing ratio of up to 18% in widespread areas and regionally up to 40% compared to a model run without bromine chemistry. A lower limit approach for the marine boundary layer, that does not explicitly include the release of halogens from sea salt aerosol, shows that for dimethyl sulfide (DMS) the effect is even larger, with up to 60% reduction of its tropospheric column. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. In addition there are changes in the HO<sub>2</sub>:OH ratio that also affect NO<sub>x</sub> and PAN. These results imply that potentially significant strong sinks for O<sub>3</sub> and DMS have so far been ignored in many studies of the chemistry of the troposphere.
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A new Lagrangian method is proposed to quantify the transport of ozone – or any other atmospheric constituent – by objectively-defined air-masses. In the framework of mesoscale modelling, this method is an alternative to classical Eulerian or trajectory-based methods, which suffer from many drawbacks at this scale. The elementary air-parcels are tagged with their initial location (what is made possible in the model by passive transport of three tracer fields initialized with the space coordinates). This enables to retrieve not only their back-trajectories but also their physical and chemical history. This information is in turn used to relevantly define transporting air-masses along objective criteria. For instance the ozone mass that has left the planetary boundary layer (PBL) to intrude the free troposphere (FT) in a given time interval, is carried by the ensemble of air-parcels that were initially in the PBL but are finally in the FT. Such an air-mass can be characterized by e.g., a criterion on the initial and final values of the turbulent kinetic energy of the air-parcels. The last step to obtain the sought ozone mass is a simple spatial integration of the ozone concentration over the so-defined air-mass. Two case-studies are presented as illustrations with increasing complexity: (i) the downward transport of ozone accompanying a tropopause fold, across a mid-tropospheric altitude level; (ii) a case of PBL-to-FT transport, as evoked above.
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The topic of this paper is the sensitivity of the brightness of noctilucent clouds (NLC) on the ambient water vapour mixing ratio f(H<sub>2</sub>O). Firstly, we use state-of-the-art models of NLC layer formation to predict NLC brightness changes in response to changes in the 80km mixing ratio f(H<sub>2</sub>O) for the two cases of ground-based 532nm lidar observations at 69° N and for hemispheric satellite SBUV observations at 252nm wavelength. In this study, we include a re-evaluation of the sensitivity of NLC brightness to changes in solar Lyman α flux. Secondly, we review observations of episodic changes in f(H<sub>2</sub>O) and those in NLC brightness, the former being available since 1992, the latter since 1979. To this review, we add a new series of observations of f(H<sub>2</sub>O), performed in the Arctic summer at the ALOMAR observatory. The episodic change exhibited by the Arctic summer means of f(H<sub>2</sub>O) turns out to be quite different from all those derived from annual means of f(H<sub>2</sub>O). The latter indicate that since 1996 a significant reduction of annually averaged upper mesospheric water vapour has occurred at low, mid, and high latitudes. These decreases of f(H<sub>2</sub>O) have been observed over the same time period in which a slow increase of SBUV NLC albedo has occurred. From this scenario and additional arguments we conclude that the cause for the observed long-term increase in NLC albedo remains to be identified. We close with comments on the very different character of decadal variations in NLC brightness and occurrence rate.
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A Saharan dust event was observed in a rural area in the Maurienne Valley (French Alps) in summer 2000. Detailed data on PM<sub>10</sub>, particle numbers, and aerosol chemistry (ionic species and Elemental Carbon (EC) and Organic Carbon (OC)) are presented. The comparative evolutions of particle numbers and chemistry (calcium, sodium, and sulfate) show that the overall period included two episodes of dust particles with very distinct chemistry, followed by an episode with a large increase of the concentrations of species with an anthropogenic origin. The overall data set does not indicate large interactions between the dust particles and compounds from anthropogenic origin (sulfate, nitrate) or with organic carbon, all of these species showing very low concentrations. Simplistic calculations indicate that these concentrations are consistent with our current knowledge of adsorption processes of gases on mineral dust in a clean air mass.
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Ice crystals were grown in the laboratory at −15°C, at different growth rates and in the presence of a partial pressure of HCl of 1.63×10<sup>-3</sup> Pa, to test whether the ice growth rate influences the amount of HCl taken up, <i>X</i><sub>HCl</sub>, as predicted by the ice growth mechanism of Domine and Thibert (1996). The plot of HCl concentration in ice as a function of growth rate has the aspect predicted by that mechanism: <i>X</i><sub>HCl</sub> decreases with increasing growth rate, from a value that depends on thermodynamic equilibrium to a value that depends only on kinetic factors. The height of the growth steps of the ice crystals is determined to be about 150 nm from these experiments. We discuss that the application of these laboratory experiments to cloud ice crystals and to snow metamorphism is not quantitatively possible at this stage, because the physical variables that determine crystal growth in nature, and in particular the step height, are not known. Qualitative applications are attempted for HCl and HNO<sub>3</sub> incorporation in cloud ice and snowpack crystals.
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The formation and growth of atmospheric aerosols depend on several steps, namely nucleation, initial steps of growth and subsequent – mainly condensational – growth. This work focuses on the initial steps of growth, meaning the growth right after nucleation, where the interplay of curvature effects and thermodynamics has a significant role on the growth kinetics. More specifically, we investigate how ion clusters and aerosol particles grow from 1.5 nm to 20 nm (diameter) in atmospheric conditions using experimental data obtained by air ion and aerosol spectrometers. The measurements have been performed at a boreal forest site in Finland. The observed trend that the growth rate seems to increase as a function of size can be used to investigate possible growth mechanisms. Such a growth rate is consistent with a recently suggested nano-Köhler mechanism, in which growth is activated at a certain size with respect to condensation of organic vapors. The results also imply that charge-enhanced growth associated with ion-mediated nucleation plays only a minor role in the initial steps of growth, since it would imply a clear decrease of the growth rate with size. Finally, further evidence was obtained on the earlier suggestion that atmospheric nucleation and the subsequent growth of fresh nuclei are likely to be uncoupled phenomena via different participating vapors.
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A mass balance inverse modelling procedure is applied with a time-dependent methane concentration boundary condition and a chemical transport model to relate observed changes in the surface distribution of methane mixing ratios during the 1990s to changes in its surface sources. The model reproduces essential features of the global methane cycle, such as the latitudinal distribution and seasonal cycle of fluxes, without using a priori knowledge of methane fluxes. A detailed description of the temporal and spatial variability of the fluxes diagnosed by the inverse procedure is presented, and compared with previously hypothesised changes in the methane budget, and previous inverse modelling studies. The sensitivity of the inverse results to the forcing data supplied by surface measurements of methane from the NOAA CMDL cooperative air sampling network is also examined. This work serves as an important starting point for future inverse modelling work examining changes in both the source and sink terms in the methane budget together.
