ALBERT

Description: Snow, through its trace constituents, can have a major impact on lower tropospheric chemistry, as evidenced by ozone depletion events (ODEs) in oceanic polar areas. These ODEs are caused by the chemistry of bromine compounds that originate from sea salt bromide. Bromide may be supplied to the snow surface by upward migration from sea ice, by frost flowers being wind-blown to the snow surface, or by wind-transported aerosol generated by sea spray. We investigate here the relative importance of these processes by analyzing ions in snow near Alert and Ny-Ålesund (Canadian and European high Arctic) in winter and spring. Vertical ionic profiles in the snowpack on sea ice are measured to test upward migration of sea salt ions and to seek evidence for ion fractionation processes. Time series of the ionic composition of surface snow layers are investigated to quantify wind-transported ions. Upward migration of unfractionated sea salt to heights of at least 17cm was observed in winter snow, leading to Cl- concentration of several hundred µM. Upward migration thus has the potential to supply ions to surface snow layers. Time series show that wind can deposit aerosols to the top few cm of the snow, leading also to Cl- concentrations of several hundred µM, so that both diffusion from sea ice and wind transport can significantly contribute ions to snow. At Ny-Ålesund, sea salt transported by wind was unfractionated, implying that it comes from sea spray rather than frost flowers. Estimations based on our results suggest that the marine snowpack contains about 10 times more Na+ than the frost flowers, so that both the marine snowpack and frost flowers need to be considered as sea salt sources. Our data suggest that ozone depletion chemistry can significantly enhance the Br- content of snow. We speculate that this can also take place in coastal regions and contribute to propagate ODEs inland. Finally, we stress the need to measure snow physical parameters such as permeability and specific surface area to understand quantitatively changes in snow chemistry.

Description: The results of two methods retrieving actinic flux and ozone photolysis frequencies (JO1D), from measurements of irradiance with a Brewer MKIII spectroradiometer are investigated in this paper. The first method uses actinic flux retrieved from irradiance measurements by the use of known formulas while the second is an empirical method converting irradiance to JO1D through polynomials extracted from a study of synchronous actinic flux and irradiance measurements. When examining the actinic fluxes derived from the first method to those measured by an actinic flux spectrometer data agree within ±10% for solar zenith angles lower than 75° for the UV-B and the UV-A wavelength band. Also, the actinic to global irradiance ratio derived, deviates within ±6% for solar zenith angles lower than 70° compared with cloudless sky calculations of the TUV model. For both cases the deviations are in the order of the magnitude of the measurement or model uncertainties. Values of JO1D calculated by the second method show a mean ratio of 0.99±0.10 (1σ) and 0.98±0.06 for all data and for cloudless skies respectively when compared with values of JO1D derived by a Bentham actinic flux spectroradiometer. Finally, the agreement of the two methods is within ±5% comparing two years' data of JO1D retrieved from irradiance measurements at Thessaloniki, Greece. The use of such methods on extensive data sets of global irradiance can provide JO1D values with acceptable uncertainty, a parameter of particular importance for chemical process studies.

Description: A new 3-D mercury model has been developed within the Danish Arctic Monitoring and Assessment Programme (AMAP). The model is based on the Danish Eulerian Hemispheric Model, which in the original version has been used to study the transport of SO2, SO42- and Pb into the Arctic. It was developed for sulphur in 1990 and in 1999 also lead was included. For the current study a chemical scheme for mercury has been included and the model is now applied to the mercury transport problem. Some experiments with the formulation of the mercury chemistry during the Polar Sunrise are carried out in order to investigate the observed depletion. Some of the main conclusions of the work described in this paper are that atmospheric transport of mercury is a very important pathway into the Arctic and that mercury depletion in the Arctic troposphere during the Polar Sunrise contributes considerably to the deposition of mercury in the Arctic.

Description: Photolysis of water-soluble components inside cloud droplets by ultraviolet/visible radiation may play an important role in atmospheric chemistry. Two earlier studies have suggested that the actinic flux and hence the photolysis frequency within spherical droplets is enhanced relative to that in the surrounding air, but have given different values for this enhancement. Here, we reconcile these discrepancies by noting slight errors in both studies that, when corrected, lead to consistent results. Madronich (1987) examined the geometric (large droplet) limit and concluded that refraction leads to an enhancement factor, averaged over all incident directions, of 1.56. However, the physically relevant quantity is the enhancement of the average actinic flux (rather than the average enhancement factor) which we show here to be 1.26 in the geometric limit. Ruggaber et al. (1997) used Mie theory to derive energy density enhancements slightly larger than 2 for typical droplet sizes, and applied these directly to the calculation of photolysis rates. However, the physically relevant quantity is the actinic flux (rather than the energy density) which is obtained by dividing the energy density by the refractive index of water, 1.33. Thus, the Mie-predicted enhancement for typical cloud droplet sizes is in the range 1.5, only coincidentally in agreement with the value originally given by Madronich. We also investigated the influence of resonances in the actinic flux enhancement. These narrow spikes which are resolved only by very high resolution calculations are orders of magnitude higher than the intermediate values but contribute only little to the actinic flux enhancement when averaged over droplet size distributions. Finally, a table is provided which may be used to obtain the actinic flux enhancement for the photolysis of any dissolved species.

Description: Trends in derived from a 45 year integration of a chemistry-climate model (CCM) run have been compared with ground-based measurements at Lauder (45° S) and Arrival Heights (78° S). Observed trends in at both sites exceed the modelled trends in N2O, the primary source gas for stratospheric NO2. This suggests that the processes driving the trend are not solely dictated by changes in but are coupled to global atmospheric change, either chemically or dynamically or both. If CCMs are to accurately estimate future changes in ozone, it is important that they comprehensively include all processes affecting NOx (NO+NO2) because NOx concentrations are an important factor affecting ozone concentrations. Comparison of measured and modelled NO2 trends is a sensitive test of the degree to which these processes are incorporated in the CCM used here. At Lauder the 1980-2000 CCM NO2 trends (4.2% per decade at sunrise, 3.8% per decade at sunset) are lower than the observed trends (6.5% per decade at sunrise, 6.0% per decade at sunset) but not significantly different at the 2σ level. Large variability in both the model and measurement data from Arrival Heights makes trend analysis of the data difficult. CCM predictions (2001-2019) of NO2 at Lauder and Arrival Heights show significant reductions in the rate of increase of NO2 compared with the previous 20 years (1980-2000). The model results indicate that the partitioning of oxides of nitrogen changes with time and is influenced by both chemical forcing and circulation changes.

Description: Smoke-haze episodes caused by vegetation and peat fires affect parts of Indonesia every year with significant impacts on human health and climate. Particularly fires in degenerated peat areas release huge amounts of trace gases, e.g. CO2, CO and CH4, and particles into the atmosphere, exceeding by far the emissions per unit area from fires in surface vegetation. However, only limited information is available about the current distribution of pristine and degenerated peat areas in Indonesia, their depth, drainage condition and modification by fire. Particularly during the strong El Niño event in 1997/1998 a huge uncertainty exists about the contribution of Indonesian peat fire emissions to the measured increase of atmospheric CO2, as the published estimates of the peat area burned differ considerably. In this paper we study the contribution of peat fire emissions in Indonesia during the El Niño event 1997/1998. A regional three-dimensional atmosphere-chemistry model is applied over Indonesia using two emission estimates. These vegetation and peat fire emission inventories for Indonesia are set up in 0.5° resolution in weekly intervals and differ only in the size of the fire affected peat areas. We evaluate simulated rainfall and particle concentrations by comparison with observations to draw conclusions on the total carbon emissions released from the vegetation and peat fires in Indonesia in 1997/1998.

Description: Water vapour has been measured from the International Scientific Station Jungfraujoch (ISSJ, 47° N, 7° E, 3580m above sea level) during the winters of 1999/2000 and 2000/2001 by microwave radiometry and Raman lidar. The abundance of atmospheric water vapour between the planetary boundary layer and the upper stratosphere varies over more than three orders of magnitude. The currently used measurement techniques are only suited to determine the abundance of water vapour in different atmospheric regimes. None can resolve the vertical distribution profile from ground level to the top of the stratosphere by itself. We present such a water vapour profile where simultaneous measurements from a Raman lidar and a microwave radiometer were combined to cover both the troposphere and the stratosphere, respectively. We also present a study of the stratospheric and tropospheric water vapour variability for the two consecutive winters.

Description: Explicit mechanisms describing the complex degradation pathways of atmospheric volatile organic compounds (VOCs) are important, since they allow the study of the contribution of individual VOCS to secondary pollutant formation. They are computationally expensive to solve however, since they contain large numbers of species and a wide range of time-scales causing stiffness in the resulting equation systems. This paper and the following companion paper describe the application of systematic and automated methods for reducing such complex mechanisms, whilst maintaining the accuracy of the model with respect to important species and features. The methods are demonstrated via application to version 2 of the Leeds Master Chemical Mechanism. The methods of Jacobian analysis and overall rate sensitivity analysis proved to be efficient and capable of removing the majority of redundant reactions and species in the scheme across a wide range of conditions relevant to the polluted troposphere. The application of principal component analysis of the rate sensitivity matrix was computationally expensive due to its use of the decomposition of very large matrices, and did not produce significant reduction over and above the other sensitivity methods. The use of the quasi-steady state approximation (QSSA) proved to be an extremely successful method of removing the fast time-scales within the system, as demonstrated by a local perturbation analysis at each stage of reduction. QSSA species were automatically selected via the calculation of instantaneous QSSA errors based on user-selected tolerances. The application of the QSSA led to the removal of a large number of alkoxy radicals and excited Criegee bi-radicals via reaction lumping. The resulting reduced mechanism was shown to reproduce the concentration profiles of the important species selected from the full mechanism over a wide range of conditions, including those outside of which the reduced mechanism was generated. As a result of a reduction in the number of species in the scheme of a factor of 2, and a reduction in stiffness, the computational time required for simulations was reduced by a factor of 4 when compared to the full scheme.

Description: Chemical ozone loss in the Arctic stratosphere was investigated for the twelve years between 1991 and 2003 employing the ozone-tracer correlation method. For this method, the change in the relation between ozone and a long-lived tracer is considered for all twelve years over the lifetime of the polar vortex to calculate chemical ozone loss. Both the accumulated local ozone loss in the lower stratosphere and the column ozone loss were derived consistently, mainly on the basis of HALOE satellite observations. HALOE measurements do not cover the polar region homogeneously over the course of the winter. Thus, to derive an early winter reference function for each of the twelve years, all available measurements were additionally used; for two winters climatological considerations were necessary. Moreover, a detailed quantification of uncertainties was performed. This study further demonstrates the interaction between meteorology and ozone loss. The connection between temperature conditions and chlorine activation, and in turn, the connection between chlorine activation and ozone loss, becomes obvious in the HALOE HCl measurements. Additionally, the degree of homogeneity of ozone loss within the vortex was shown to depend on the meteorological conditions. Results derived here are in general agreement with the results obtained by other methods for deducing polar ozone loss. Differences occur mainly owing to different time periods considered in deriving accumulated ozone loss. However, very strong ozone losses as deduced from SAOZ for January in winters 1993-1994 and 1995-1996 cannot be identified using available HALOE observations in the early winter. In general, strong accumulated ozone loss was found to occur in conjunction with a strong cold vortex containing a large volume of possible PSC existence (VPSC), whereas moderate ozone loss was found if the vortex was less strong and moderately warm. Hardly any ozone loss was calculated for very warm winters with small amounts of VPSC during the entire winter. This study supports the linear relationship between VPSC and the accumulated ozone loss reported by Rex et al. (2004) if VPSC was averaged over the entire winter period. Here, further meteorological factors controlling ozone loss were additionally identified if VPSC was averaged over the same time interval as that for which the accumulated ozone loss was deduced. A significant difference in ozone loss (of ≈36DU) was found due to the different duration of solar illumination of the polar vortex of at maximum 4 hours per day in the observed years. Further, the increased burden of aerosols in the atmosphere after the Pinatubo volcanic eruption in 1991 significantly increased the extent of chemical ozone loss.

Description: During the calendar years 1998-2002, 147 clear 8nm diameter particle formation events have been identified at the SMEAR I station in Värriö, northern Finland. The events have been classified in detail according to the particle formation rate, growth rate, event starting time, different trace gas concentrations and pre-existing particle concentrations as well as various meteorological conditions. The frequency of particle formation and growth events was highest during the spring months between March and May, suggesting that increasing biological activity might produce the precursor gases for particle formation. The apparent 8nm particle formation rates were around 0.1 /cm3s, and they were uncorrelated with growth rates that varied between 0.5 and 10nm/h. The air masses with clearly elevated sulphur dioxide concentrations (above 1.6ppb) came, as expected, from the direction of the Nikel and Monschegorsk smelters. Only 15 formation events can be explained by the pollution plume from these sources.

Description: Forest fire emissions have a strong impact on the concentrations of trace gases and aerosols in the atmosphere. In order to quantify the influence of boreal forest fire emissions on the atmospheric composition, the fire seasons of 1997 and 1998 are compared in this paper. Fire activity in 1998 was very strong, especially over Canada and Eastern Siberia, whereas it was much weaker in 1997. According to burned area estimates the burning in 1998 was more than six times as intense as in 1997. Based on hot spot locations derived from ATSR (Along Track Scanning Radiometer) data and official burned area data, fire emissions were estimated and their transport was simulated with a Lagrangian tracer transport model. Siberian and Canadian forest fire tracers were distinguished to investigate the transport of both separately. The fire emissions were transported even over intercontinental distances. Due to the El Niño induced meteorological situation, transport from Siberia to Canada was enhanced in 1998. Siberian fire emissions were transported towards Canada and contributed concentrations more than twice as high as those due to Canada's own CO emissions by fires. In 1998 both tracers arrive at higher latitudes over Europe, which is due to a higher North Atlantic Oscillation (NAO) index in 1998. The simulated emission plumes are compared to CMDL (Climate Monitoring and Diagnostics Laboratory) CO2 and CO data, Total Ozone Mapping Spectrometer (TOMS) aerosol index (AI) data and Global Ozone Monitoring Experiment (GOME) tropospheric NO2 and HCHO columns. All the data show clearly enhanced signals during the burning season of 1998 compared to 1997. The results of the model simulation are in good agreement with ground-based as well as satellite-based measurements.

Description: Here we present a concise and efficient algorithm to mimic the growth and sedimentation of Nitric Acid Trihydate (NAT) particles in the polar vortex in a state-of-the-art 3D chemistry transport model. The particle growth and sedimentation are calculated using the microphysical formulation of Carslaw et al. (2002). Once formed, NAT particles are transported in the model as tracers in the form of size-segregated quantities or size bins. Two different approaches were adopted for this purpose: one assuming a fixed particle number density ("FixedDens") and the other assuming a discrete set of particle diameter values ("FixedRad"). Simulations were performed for three separate 10-day periods during the 1999-2000 Arctic winter and compared to the results of an existing Lagrangian model study, which uses similar microphysics in a computationally more expensive method for the simulation of NAT particle growth. The resulting particle sizes for both our approaches compare favourably at 430K with those obtained from this previous model study, and also in-situ observations related to the size of large NAT particles. The particle growth is faster for "FixedDens" resulting in a difference in (de)nitrification by a factor of ~2 for all three simulation periods. Comparisons were made with a standard equilibrium approach and the differences in the redistribution of HNO3 were found to be substantial. For both approaches the performance of the algorithm is rather insensitive to both the number of size bins and the shape of the size distribution, and show a weak dependence on the prescribed total particle number density during the coldest period. This results in an increase of 7% for the "FixedRad" approach and 17% for the "FixedDens" approach when increasing the total particle number density by a factor of 2.5.

Description: We show that mineral dust optical depth and altitude can be retrieved from the Aqua - Advanced Infrared Radiation Sounder (AIRS) measurements. Sensitivity studies performed with a high spectral resolution radiative transfer code show that dust effect on brightness temperatures may reach about 10 Kelvins for some channels. Using a Look-Up-Table approach, we retrieve not only the 10 µm optical depth but also the altitude of Saharan dust layer, above the Atlantic Ocean, from April to September 2003. A key point of our method is its ability to retrieve dust altitude from satellite observations. The time and space distribution of the optical depth is in good agreement with the Moderate resolution Imaging Spectroradiometer (MODIS) products. Comparing MODIS and AIRS aerosol optical depths, we find that the ratio between infrared and visible optical depths decreases during transport from 0.35 to 0.22, revealing a loss in coarse particles caused by gravitational settling. The evolution of dust altitude from spring to summer is in agreement with current knowledge on transport seasonality.

Description: Future increases in the concentration of greenhouse gases and water vapour may cool the stratosphere further and increase the amount of polar stratospheric clouds (PSCs). Future Arctic PSC areas have been extrapolated from the highly significant trends 1958-2001. Using a tight correlation between PSC area and the total vortex ozone depletion and taking the decreasing amounts of ozone depleting substances into account we make empirical estimates of future ozone. The result is that Arctic ozone losses increase until 2010-2015 and decrease only slightly afterwards. However, for such a long extrapolation into the future caution is necessary. Tentatively taking the modelled decrease in the ozone trend in the future into account results in almost constant ozone depletions until 2020 and slight decreases afterwards. This approach is a complementary method of prediction to that based on the complex coupled chemistry-climate models (CCMs).

Description: A polar stratospheric ice cloud (PSC type II) was observed by airborne lidar above Greenland on 14 January 2000. It was the unique observation of an ice cloud over Greenland during the SOLVE/THESEO 2000 campaign. Mesoscale simulations with the hydrostatic HRM model are presented which, in contrast to global analyses, are capable to produce a vertically propagating gravity wave that induces the low temperatures at the level of the PSC afforded for the ice formation. The simulated minimum temperature is ~8 K below the driving analyses and ~4.5 K below the frost point, exactly coinciding with the location of the observed ice cloud. Despite the high elevations of the Greenland orography the simulated gravity wave is not a mountain wave. Analyses of the horizontal wind divergence, of the background wind profiles, of backward gravity wave ray-tracing trajectories, of HRM experiments with reduced Greenland topography and of several diagnostics near the tropopause level provide evidence that the wave is emitted from an intense, rapidly evolving, anticyclonically curved jet stream. The precise physical process responsible for the wave emission could not be identified definitely, but geostrophic adjustment and shear instability are likely candidates. In order to evaluate the potential frequency of such non-orographic polar stratospheric cloud events, the non-linear balance equation diagnostic is performed for the winter 1999/2000. It indicates that ice-PSCs are only occasionally generated by gravity waves emanating from spontaneous adjustment.

Description: A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd), canopy resistances (Rc) and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3) fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only) using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+]) of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

Description: A Fresnel transform technique has been developed at Adelaide to analyse radar meteor echoes detected in the transverse mode. The genesis for this technique was the study of the structure of the scattering ionization immediately behind the head of the trail, in order to deduce the degree of fragmentation of the ablating meteoroid. The technique has been remarkably successful in not only giving insight into the fragmentation of meteoroids, but also revealing other significant features of the trails including diffusion, lateral motion of the trail during formation due to wind drift, and phase of the scattered signal in the vicinity of the head of the trail. A serendipitous outcome of the analysis is the measurement of the speed and deceleration of the meteoroid producing the trail to a precision far exceeding that available from any other method applied to transverse scatter data. Examples of the outcomes of the technique applied to meteor echoes obtained with a 54MHz narrow beam radar are presented.

Description: It is commonly believed that cumulus convection preferentially generates gravity waves with tropospheric vertical wavelengths approximately twice the depth of the convective heating. Individual cumulonimbus, however, act as short term transient heat sources (duration 10 to 30min). Gravity waves generated by such sources have broad frequency spectra and a wide range of vertical scales. The high-frequency components tend to have vertical wavelengths much greater than twice the depth of the heating. Such waves have large vertical group velocities, and are only observed for a short duration and at short horizontal distances from the convective source. At longer times and longer distances from the source the dominant wave components have short vertical wavelengths and much slower group velocities, and thus are more likely to be observed even though their contribution to the momentum flux in the upper stratosphere and mesosphere may be less than that of the high frequency waves. These properties of convectively generated waves are illustrated by a linear numerical model for the wave response to a specified transient heat source. The wave characteristics are documented through Fourier and Wavelet analysis, and implications for observing systems are discussed.

Description: As part of the OSOA (Origin and formation of Secondary Organic Aerosols) project, two intensive field campaigns were conducted in Melpitz, Germany and Hyytiälä, Finland. This paper gives an overview of the measurements made during the Hyytiälä campaign, which was held between 1 and 16 August 2001. Various instrumental techniques were used to achieve physical and chemical characterisation of aerosols and to investigate possible precursor gases. During the OSOA campaign in Hyytiälä, particle formation was observed on three consecutive days at the beginning of the campaign (1 to 3 August 2001) and on three days later on. The investigation of the meteorological situation divided the campaign into two parts. During the first three days of August, relatively cold and clean air masses from northwest passed over the station (condensation sink – CS:

Description: A modelling study of the formation of volatile particles in a combustor exhaust has been carried out in the frame of the PartEmis European project. A kinetic model has been used in order to investigate nucleation efficiency of the H2O-H2SO4 binary mixture in the sampling system. A value for the fraction of the fuel sulphur S(IV) converted into S(VI) has been indirectly deduced from comparisons between model results and measurements. In the present study, ranges between roughly 2.5% and 6%, depending on the combustor settings and on the value assumed for the parameter describing sulphuric acid wall losses. Soot particles hygroscopicity has also been investigated as their activation is a key parameter for contrail formation. Growth factors of monodisperse particles exposed to high relative humidity (95%) have been calculated and compared with experimental results. The modelling study confirms that the growth factor increases as the soot particle size decreases.

Description: We use a genetic algorithm to construct optimal observing networks of atmospheric concentration for inverse determination of net sources. Optimal networks are those that produce a minimum in average posterior uncertainty plus a term representing the divergence among source estimates for different transport models. The addition of this last term modifies the choice of observing sites, leading to larger networks than would be chosen under the traditional estimated variance metric. Model-model differences behave like sub-grid heterogeneity and optimal networks try to average over some of this. The optimization does not, however, necessarily reject apparently difficult sites to model. Although the results are so conditioned on the experimental set-up that the specific networks chosen are unlikely to be the best choices in the real world, the counter-intuitive behaviour of the optimization suggests the model error contribution should be taken into account when designing observing networks. Finally we compare the flux and total uncertainty estimates from the optimal network with those from the 3 control case. The  3 control case performs well under the chosen uncertainty metric and the flux estimates are close to those from the optimal case. Thus the 3 findings would have been similar if minimizing the total uncertainty guided their network choice.

Description: Currently two polar orbiting satellite instruments measure CO2 concentrations in the Earth's atmosphere, while other missions are planned for the coming years. In the future such instruments might become powerful tools for monitoring changes in the atmospheric CO2 abundance and to improve our quantitative understanding of the leading processes controlling this. At the moment, however, we are still in an exploratory phase where first experiences are collected and promising new space-based measurement concepts are investigated. This study assesses the potential of some of these concepts to improve CO2 source and sink estimates obtained from inverse modelling. For this purpose the performance of existing and planned satellite instruments is quantified by synthetic simulations of their ability to reduce the uncertainty of the current source and sink estimates in comparison with the existing ground-based network of sampling sites. Our high resolution inversion of sources and sinks (at 8°x10°) allows us to investigate the variation of instrument performance in space and time and at various temporal and spatial scales. The results of our synthetic tests clearly indicate that the satellite performance increases with increasing sensitivity of the instrument to CO2 near the Earth's surface, favoring the near infra-red technique. Thermal infrared instruments, on the contrary, reach a better global coverage, because the performance in the near infrared is reduced over the oceans owing to a low surface albedo. Near infra-red sounders can compensate for this by measuring in sun-glint, which will allow accurate measurements over the oceans, at the cost, however, of a lower measurement density. Overall, the sun-glint pointing near infrared instrument is the most promising concept of those tested. We show that the ability of satellite instruments to resolve fluxes at smaller temporal and spatial scales is also related to surface sensitivity. All the satellite instruments performed relatively well over the continents resulting mainly from the larger prior flux uncertainties over land than over the oceans. In addition, the surface networks are rather sparse over land increasing the additional benefit of satellite measurements there. Globally, challenging satellite instrument precisions are needed to compete with the current surface network (about 1ppm for weekly and 8°x10° averaged SCIAMACHY columns). Regionally, however, these requirements relax considerably, increasing to 5ppm for SCIAMACHY over tropical continents. This points not only to an interesting research area using SCIAMACHY data, but also to the fact that satellite requirements should not be quantified by only a single number. The applicability of our synthetic results to real satellite instruments is limited by rather crude representations of instrument and data retrieval related uncertainties. This should receive high priority in future work.

Description: Formation of binary cluster ions from polar vapours is considered. The effect of vapour polarity on the size and composition of the critical clusters is investigated theoretically and a corrected version of classical Kelvin-Thomson theory of binary ion-induced nucleation is derived. The model predictions of the derived theory are compared to the results given by classical binary homogeneous nucleation theory and ion-induced nucleation theory. The calculations are performed in wide range of the ambient conditions for a system composed of sulfuric acid and water vapour. It is shown that dipole-charge interaction significantly decreases the size of the critical clusters, especially under the atmospheric conditions when the size of critical clusters is predicted to be small.

Description: The chemistry of peroxynitric acid (HO2NO2) and methyl peroxynitrate (CH3O2NO2)is predicted to be particularly important in the upper troposphere where temperatures are frequently low enough that these compounds do not rapidly decompose. At temperatures below 240K, we calculate that about 20% of NOy in the mid- and high-latitude upper troposphere is HO2NO2. Under these conditions, the reaction of OH with HO2NO2 is estimated to account for as much as one third of the permanent loss of hydrogen radicals. During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign, we used thermal dissociation laser-induced fluorescence (TD-LIF) to measure the sum of peroxynitrates (PNs HO2NO2+CH3O2NO2+PAN+PPN+...) aboard the NCAR C-130 research aircraft. We infer the sum of HO2NO2 and CH3O2NO2 as the difference between PN measurements and gas chromatographic measurements of the two major peroxy acyl nitrates, peroxy acetyl nitrate (PAN) and peroxy propionyl nitrate (PPN). Comparison with NOy and other nitrogen oxide measurements confirms the importance of HO2NO2 and CH3O2NO2 to the reactive nitrogen budget and shows that current thinking about the chemistry of these species is approximately correct. During the spring high latitude conditions sampled during the TOPSE experiment, the model predictions of the contribution of (HO2NO2+CH3O2NO2) to NOy are highly temperature dependent: on average 30% of NOy at 230K, 15% of NOy at 240K, and 5% of NOy above 250K. The temperature dependence of the inferred concentrations corroborates the contribution of overtone photolysis to the photochemistry of peroxynitric acid. A model that includes IR photolysis (J=1x10-5s-1) agreed with the observed sum of HO2NO2+CH3O2NO2 to better than 35% below 240K where the concentration of these species is largest.

Description: The potential enhancement of tropospheric column ozone values over the Tropical Atlantic Ocean on a seasonal basis by lightning is investigated using satellite derived ozone data, TRMM lightning data, ozonesonde data and NCEP reanalysis during 1998-2001. Our results show that the number of lightning flashes in Africa and South America reach a maximum during September, October and November (SON). The spatial patterns of winds in combination with lightning from West Africa, Central Africa and South America is likely responsible for enriching middle/upper troposphere ozone over the Tropical South Atlantic during SON. Moreover, lightning flashes are high in the hemisphere opposite to biomass burning during December, January, and February (DJF) and June, July and August (JJA). This pattern leads to an enrichment of ozone in the middle/upper troposphere in the Southern Hemisphere Tropics during DJF and the Northern Hemisphere Tropics during JJA. During JJA the largest numbers of lightning flashes are observed in West Africa, enriching tropospheric column ozone to the north of 5S in the absence of biomass burning. During DJF, lightning is concentrated in South America and Central Africa enriching tropospheric column ozone south of the Equator in the absence of biomass burning.

Description: The main purpose of this study is to develop a methodology for a multidisciplinary nuclear risk and vulnerability assessment, and to test this methodology through estimation of a nuclear risk to population in the Northern European countries in case of a severe accident at the nuclear risk sites. For assessment of the probabilistic risk and vulnerability, a combination of social-geophysical factors and probabilities are considered. The main focus of this paper is the description of methodology for evaluation of the atmospheric transport of radioactive releases from the risk site regions based on the long-term trajectory modeling. The suggested methodology is given from the probabilistic point of view. The main questions stated are: What are probabilities and times for radionuclide atmospheric transport to different neighbouring countries and territories in case of the hypothetical accidental release at the nuclear risk site? Which geographical territories or countries are at the highest risk from the hypothetical accidental releases? To answer these questions we suggest applying the following research tools for probabilistic atmospheric studies. First tool is atmospheric modelling to calculate multiyear forward trajectories originated over the sites. Second tool is statistical analyses to explore temporal and spatial structure of calculated trajectories and evaluate different probabilistic impact indicators: atmospheric transport pathways, airflow, fast transport, typical transport time, maximum possible impact zone, maximum reaching distance, etc. These indicators are applicable for further GIS-analysis and integration to estimate regional risk and vulnerability in case of accidental releases at the risk sites and for planning the emergency response and preparedness systems.

Description: Determining the velocity of meteoroids as they enter the Earth's atmosphere is very important since the value is fundamental in calculating the orbit of the meteoroid and hence eventually its origin. We describe early attempts at this determination and highlight problems that exist today.

Description: In a recent published paper, Generoso et al. (2003) describe a method for improving the spatial and temporal distribution of pyrogenic aerosol emission inventories. In the course of their analysis, the authors note several significant discrepancies in the seasonality of burning as observed by the Visible and Infrared Scanner (VIRS) and four other biomass burning data sets derived from satellite observations. In this commentary we explain the source of these discrepancies and clarify the origin of the VIRS observations that were used by Generoso et al.

Description: An assessment of the accuracy of OH concentrations measured in a smog chamber by a calibrated laser-induced fluorescence (LIF) instrument has been made, in the course of 9 experiments performed to study the photo-oxidation of benzene, toluene, 1,3,5-trimethylbenzene, para-xylene, ortho-cresol and ethene at the European Photoreactor facility (EUPHORE). The LIF system was calibrated via the water photolysis / ozone actinometry approach. OH concentrations were inferred from the instantaneous rate of removal of each hydrocarbon species (measured by FTIR or HPLC) via the appropriate rate coefficient for their reaction with OH, and compared with those obtained from the LIF system. Good agreement between the two approaches was found for all species with the exception of 1,3,5-trimethylbenzene, for which OH concentrations inferred from hydrocarbon removal were a factor of 3 lower than those measured by the LIF system. From the remaining 8 experiments, an overall value of 1.15±0.13 (±1σ) was obtained for [OH]LIF / [OH]Hydrocarbon Decay, compared with the estimated uncertainty in the accuracy of the water photolysis / ozone actinometry OH calibration technique of 26% (1σ).

Description: A set of 813 lidar profiles of tropospheric aerosol and cirrus clouds extinction and depolarization observed in Rome, Italy, between February 2001 and February 2002 is analyzed and discussed. The yearly record reveals a meaningful contribution of both cirrus clouds (38%) and Saharan dust (12%) to the total optical thickness (OT) of 0.26, at 532nm. Seasonal analysis shows the planetary boundary layer (PBL) aerosols to be confined below 2km in winter and 3.8km in summer, with relevant OT shifting from 0.08 to 0.16, respectively. Cirrus clouds maximise in spring and autumn, in both cases with average OT similar to the PBL aerosols one. With the exception of winter months, Saharan dust is found to represent an important third layer mostly residing between PBL aerosols and cirrus clouds, with yearly average OT0.03. Saharan dust and cirrus clouds were detected in 20% and in 45% of the observational days, respectively. Validation of the lidar OT retrievals against collocated sunphotometer observations show very good agreement. These results represent one of the few yearly records of tropospheric aerosol vertical profiles available in the literature.

Description: The effect of aqueous versus crystalline sulfate-nitrate-ammonium tropospheric particles on global aerosol direct radiative forcing is assessed. A global three-dimensional chemical transport model predicts sulfate, nitrate, and ammonium aerosol mass. An aerosol thermodynamics model is called twice, once for the upper side (US) and once for lower side (LS) of the hysteresis loop of particle phase. On the LS, the sulfate mass budget is 40% solid ammonium sulfate, 12% letovicite, 11% ammonium bisulfate, and 37% aqueous. The LS nitrate mass budget is 26% solid ammonium nitrate, 7% aqueous, and 67% gas-phase nitric acid release due to increased volatility upon crystallization. The LS ammonium budget is 45% solid ammonium sulfate, 10% letovicite, 6% ammonium bisulfate, 4% ammonium nitrate, 7% ammonia release due to increased volatility, and 28% aqueous. LS aerosol water mass partitions as 22% effloresced to the gas-phase and 78% remaining as aerosol mass. The predicted US/LS global fields of aerosol mass are employed in a Mie scattering model to generate global US/LS aerosol optical properties, including scattering efficiency, single scattering albedo, and asymmetry parameter. Global annual average LS optical depth and mass scattering efficiency are, respectively, 0.023 and 10.7 m2 (g SO4-2)-1, which compare to US values of 0.030 and 13.9 m2 (g SO4-2)-1. Radiative transport is computed, first for a base case having no aerosol and then for the two global fields corresponding to the US and LS of the hysteresis loop. Regional, global, seasonal, and annual averages of top-of-the-atmosphere aerosol radiative forcing on the LS and US (FL and FU, respectively, in W m-2) are calculated. Including both anthropogenic and natural emissions, we obtain global annual averages of FL=-0.750, FU=-0.930, and DFU,L=24% for full sky calculations without clouds and FL=-0.485, FU=-0.605, and DFU,L=25% when clouds are included. Regionally, DFU,L=48% over the USA, 55% over Europe, and 34% over East Asia. Seasonally, DFU,L varies from 18% in DJF to 75% in SON over the USA. The global annual average contribution from anthropogenic aerosol is FL=-0.314 and FU=-0.404, which yield normalized direct radiative forcings (G) of GL=-205 W (g SO4-2)-1 and GU=-264 W (g SO4-2)-1.

Description: The interaction of aerosol particles composed of the protein bovine serum albumin (BSA) and the inorganic salts sodium chloride and ammonium nitrate with water vapor has been investigated by hygroscopicity tandem differential mobility analyzer (H-TDMA) experiments complemented by transmission electron microscopy (TEM) and Köhler theory calculations (100-300nm particle size range, 298K, 960hPa). BSA was chosen as a well-defined model substance for proteins and other macromolecular compounds, which constitute a large fraction of the water-soluble organic component of air particulate matter. Pure BSA particles exhibited deliquescence and efflorescence transitions at 35% relative humidity () and a hygroscopic diameter increase by up to 10% at 95% in good agreement with model calculations based on a simple parameterisation of the osmotic coefficient. Pure NaCl particles were converted from near-cubic to near-spherical shape upon interaction with water vapor at relative humidities below the deliquescence threshold (partial surface dissolution and recrystallisation), and the diameters of pure NH4NO3 particles decreased by up to 10% due to chemical decomposition and evaporation. Mixed NaCl-BSA and NH4NO3-BSA particles interacting with water vapor exhibited mobility equivalent diameter reductions of up to 20%, depending on particle generation, conditioning, size, and chemical composition (BSA dry mass fraction 10-90%). These observations can be explained by formation of porous agglomerates (envelope void fractions up to 50%) due to ion-protein interactions and electric charge effects on the one hand, and by compaction of the agglomerate structure due to capillary condensation effects on the other. The size of NH4NO3-BSA particles was apparently also influenced by volatilisation of NH4NO3, but not as much as for pure salt particles, i.e. the protein inhibited the decomposition of NH4NO3 or the evaporation of the decomposition products NH3 and HNO3. The efflorescence threshold of NaCl-BSA particles decreased with increasing BSA dry mass fraction, i.e. the protein inhibited the formation of salt crystals and enhanced the stability of supersaturated solution droplets. The H-TDMA and TEM results indicate that the protein was enriched at the surface of the mixed particles and formed an envelope, which inhibits the access of water vapor to the particle core and leads to kinetic limitations of hygroscopic growth, phase transitions, and microstructural rearrangement processes. The Köhler theory calculations performed with different types of models demonstrate that the hygroscopic growth of particles composed of inorganic salts and proteins can be efficiently described with a simple volume additivity approach, provided that the correct dry solute mass equivalent diameter and composition are known. A parameterisation for the osmotic coefficient of macromolecular substances has been derived from an osmotic pressure virial equation. For its application only the density and molar mass of the substance have to be known or estimated, and it is fully compatible with traditional volume additivity models for salt mixtures.

Description: In situ measurements of the partitioning of aerosol particles within cirrus clouds were used to investigate aerosol-cloud interactions in ice clouds. The number density of interstitial aerosol particles (non-activated particles in between the cirrus crystals) was compared to the number density of cirrus crystal residuals. The data was obtained during the two INCA (Interhemispheric Differences in Cirrus Properties from Anthropogenic Emissions) campaigns, performed in the Southern Hemisphere (SH) and Northern Hemisphere (NH) midlatitudes. Different aerosol-cirrus interactions can be linked to the different stages of the cirrus lifecycle. Cloud formation is linked to positive correlations between the number density of interstitial aerosol (Nint) and crystal residuals (Ncvi), whereas the correlations are smaller or even negative in a dissolving cloud. Unlike warm clouds, where the number density of cloud droplets is positively related to the aerosol number density, we observed a rather complex relationship when expressing Ncvi as a function of Nint for forming clouds. The data sets are similar in that they both show local maxima in the Nint range 100 to 200cm, where the SH- maximum is shifted towards the higher value. For lower number densities Nint and Ncvi are positively related. The slopes emerging from the data suggest that a tenfold increase in the aerosol number density corresponds to a 3 to 4 times increase in the crystal number density. As Nint increases beyond the ca. 100 to 200cm, the mean crystal number density decreases at about the same rate for both data sets. For much higher aerosol number densities, only present in the NH data set, the mean Ncvi remains low. The situation for dissolving clouds allows us to offer two possible, but at this point only speculative, alternative interactions between aerosols and cirrus: evaporating clouds might be associated with a source of aerosol particles, or air pollution (high aerosol number density) might retard ice particle evaporation rates.

Description: We have compared satellite and balloon observations of methane (CH4) and hydrogen fluoride (HF) during the Arctic winter 1999/2000 with results from the MA-ECHAM4 middle atmospheric general circulation model (GCM). For this purpose, the meteorology in the model was nudged towards ECMWF analyses. This nudging technique is shown to work well for this middle atmospheric model, and offers good opportunities for the simulation of chemistry and transport processes. However, caution must be used inside the polar vortex, particularly late in the winter. The current study focuses on transport of HF and CH4, initialized with satellite measurements from the HALOE instrument aboard the UARS satellite. We have compared the model results with HALOE data and balloon measurements throughout the winter, and analyzed the uncertainties associated with tracer initialization, boundary conditions and the passive tracer assumption. This comparison shows that the model represents some aspects of the Arctic vortex well, including relatively small-scale features. However, while profiles outside the vortex match observations well, the model underestimates HF and overestimates CH4 concentrations inside the vortex, particularly in the middle stratosphere. This problem is also evident in a comparison of vortex descent rates based upon vortex average tracer profiles from MA-ECHAM4, and various observations. This could be due to an underestimate of diabatic subsidence in the model, or due to too much mixing between vortex and non-vortex air.

Description: The possibility to calculate linear-source receptor relationships for the transport of atmospheric trace substances with a Lagrangian particle dispersion model (LPDM) running in backward mode is shown and presented with many tests and examples. This mode requires only minor modifications of the forward LPDM. The derivation includes the action of sources and of any first-order processes (transformation with prescribed rates, dry and wet deposition, radioactive decay, etc.). The backward mode is computationally advantageous if the number of receptors is less than the number of sources considered. The combination of an LPDM with the backward (adjoint) methodology is especially attractive for the application to point measurements, which can be handled without artificial numerical diffusion. Practical hints are provided for source-receptor calculations with different settings, both in forward and backward mode. The equivalence of forward and backward calculations is shown in simple tests for release and sampling of particles, pure wet deposition, pure convective redistribution and realistic transport over a short distance. Furthermore, an application example explaining measurements of Cs-137 in Stockholm as transport from areas contaminated heavily in the Chernobyl disaster is included.

Description: A new modelling study of the role of transition metal ions on cloud chemistry has been performed. Developments of the Model of Multiphase Cloud Chemistry (M2C2; Leriche et al., 2001) are described, including the transition metal ions reactivity emission/deposition processes and variable photolysis in the aqueous phase. The model is then applied to three summertime scenarios under urban, remote and marine conditions, described by Ervens et al. (2003). Chemical regimes in clouds are analyzed to understand the role of transition metal ions on cloud chemistry and especially, on HxOy chemistry, which consequently influences the sulphur and the VOCs chemistry in droplets. The ratio of Fe(II)/Fe(III) exhibits a diurnal variation with values in agreement with the available measurements of Fe speciation. In the urban case, sensitivity tests with and without TMI chemistry, show an enhancement of OH concentration in the aqueous phase when TMI chemistry is considered.

Description: Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from remaining inorganic salts and "most" hydrophilic organic matter (MHOM). This approach allowed ISOM, which constitutes the major fraction of WSOM, to be isolated from ambient aerosols and investigated in pure form. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 30% and 60% relative humidity (RH), and hygroscopic growth factors at 90% RH ranged from 1.08 to 1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. The hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75-85% and 85-95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular mass and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumed value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) ranging from +1% to -18%. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42-53 wt % of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80-62% of particulate water in the samples are associated with inorganic salts and about 20-38% with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.

Description: Polar mesosphere summer echoes (PMSE) are very strong radar echoes primarily studied in the VHF wavelength range from altitudes close to the polar summer mesopause. Radar waves are scattered at irregularities in the radar refractive index which at mesopause altitudes is effectively determined by the electron number density. For efficient scatter, the electron number density must reveal structures at the radar half wavelength (Bragg condition for monostatic radars; ~3 m for typical VHF radars). The question how such small scale electron number density structures are created in the mesopause region has been a longstanding open scientific question for almost 30 years. This paper reviews experimental and theoretical milestones on the way to an advanced understanding of PMSE. Based on new experimental results from in situ observations with sounding rockets, ground based observations with radars and lidars, numerical simulations with microphysical models of the life cycle of mesospheric aerosol particles, and theoretical considerations regarding the diffusivity of electrons in the ice loaded complex plasma of the mesopause region, a consistent explanation for the generation of these radar echoes has been developed. The main idea is that mesospheric neutral air turbulence in combination with a significantly reduced electron diffusivity due to the presence of heavy charged ice aerosol particles (radii ~5–50 nm) leads to the creation of structures at spatial scales significantly smaller than the inner scale of the neutral gas turbulent velocity field itself. Importantly, owing to their very low diffusivity, the plasma structures acquire a very long lifetime, i.e., 10 min to hours in the presence of particles with radii between 10 and 50 nm. This leads to a temporal decoupling of active neutral air turbulence and the existence of small scale plasma structures and PMSE and thus readily explains observations proving the absence of neutral air turbulence at PMSE altitudes. With this explanation at hand, it becomes clear that PMSE are a suitable tool to permanently monitor the thermal and dynamical structure of the mesopause region allowing insights into important atmospheric key parameters like neutral temperatures, winds, gravity wave parameters, turbulence, solar cycle effects, and long term changes.

Description: Aerosol size distributions have been measured at the Swedish background station Aspvreten (58.8° N, 17.4° E). Different states of the aerosol were determined using a novel application of cluster analysis. The analysis resulted in eight different clusters capturing different stages of the aerosol lifecycle. The atmospheric aerosol size distributions were interpreted as belonging to fresh, intermediate and aged types of size distribution. With aid of back trajectory analysis we present statistics concerning the relation of source area and different meteorological parameters using a non-Lagrangian approach. Source area is argued to be important although not sufficient to describe the observed aerosol properties. Especially processing by clouds and precipitation is shown to be crucial for the evolution of the aerosol size distribution. As much as 60% of the observed size distributions present features that are likely to be related to cloud processes or wet deposition. The lifetime properties of different sized aerosols are discussed by means of measured variability of the aerosol size distribution. Processing by clouds and precipitation is shown to be especially crucial in the size range 100 nm and larger. This indicates an approximate limit for activation in clouds to 100 nm in this type of environment. The aerosol lifecycle is discussed. Size distributions indicating signs of recent new particle formation (~30% of the observed size distributions) represent the first stage in the lifecycle. Aging of the aerosol size distribution may follow two branches: either growth by condensation and coagulation or processing by non-precipitating clouds. In both cases mass is accumulated. Wet removal is the main process capable of removing aerosol mass. Wet deposition is argued to be an important mechanism in reaching a state where nucleation may occur (i.e. sufficiently low aerosol surface area) in environments similar to the one studied.

Description: This paper shows that most of the so far identified constituents of the tropospheric organic particulate matter belong to a semivolatile fraction for which gas phase diffusion in the lower troposphere is sufficiently fast to establish thermodynamic equilibrium between aerosol particles. For the first time analytical expressions for this process are derived. Inspection of vapor pressure data of a series of organic substances allows a rough estimate for which substances this mixing process must be considered. As general benchmarks we conclude that for typical aerosol radii between 0.1 and 1 µm this mixing process is efficient at 25°C for polar species with molecular weights up to 200 and for non-polar species up to 320. At −10°C, these values are shifted to 150 for polar and to 270 for non-polar substances. The extent of mixing of this semivolatile fraction is governed by equilibrium thermodynamics, leading to a selectively, though not completely, internally mixed aerosol. The internal mixing leads to a systematic depression of melting and deliquescence points of organic and mixed organic/inorganic aerosols, thus leading to an aerosol population in the lower troposphere which is predominantly liquid.

Description: 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.

Description: 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.

Description: A recent World Meteorological Organisation report discussed the importance of continued study of the effect of clouds on the solar UV radiation reaching the earth's surface. The report mentions that the use of all-sky imagery offers the potential to understand and quantify cloud effects more accurately. There are an increasing number of studies investigating the enhancement of surface solar, UV irradiance, and UV actinic flux, using automated CCD and sky imagers. This paper describes new algorithms applicable to a commercially available all-sky imager (TSI-440), for research investigating cloud enhanced spectral UV irradiance. Specifically, these include three new algorithms relating to cloud amount at different spatial positions from 1) zenith and 2) from the solar position and 3) the visible brightness of clouds surrounding the sun. A possible relationship between UV enhancement and the occurrence of near-sun cloud brightness is reported based on this preliminary data. It is found that a range of wavelength dependent intensities, from 306 to 400 nm, can occur in one day for UV enhancements. Evidence for a possible decreasing variation of intensity with longer wavelengths is also presented.

Description: 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 1.63×10-3 Pa, to test whether the ice growth rate influences the amount of HCl taken up, XHCl, 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: XHCl 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 HNO3 incorporation in cloud ice and snowpack crystals.

Description: 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-1 lead to a reduction in the zonal mean O3 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 HO2:OH ratio that also affect NOx and PAN. These results imply that potentially significant strong sinks for O3 and DMS have so far been ignored in many studies of the chemistry of the troposphere.

Description: The topic of this paper is the sensitivity of the brightness of noctilucent clouds (NLC) on the ambient water vapour mixing ratio f(H2O). 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(H2O) 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(H2O) 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(H2O), performed in the Arctic summer at the ALOMAR observatory. The episodic change exhibited by the Arctic summer means of f(H2O) turns out to be quite different from all those derived from annual means of f(H2O). 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(H2O) 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.

Description: 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/m3, which corresponds to an annual mean of 0.8µg/m3 or 24% of TSP.

Description: 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 2-7x10-5sr-1. 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.

Description: A Saharan dust event was observed in a rural area in the Maurienne Valley (French Alps) in summer 2000. Detailed data on PM10, 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.

Description: Methane is a significant atmospheric trace gas in the context of greenhouse warming and climate change. The dominant sink of atmospheric methane is the hydroxyl radical (OH). Recently, a mechanism for production of chlorine radicals (Cl) in the marine boundary layer (MBL) via bromine autocatalysis has been proposed. The importance of this mechanism in producing a methane sink is not clear at present because of the difficulty of in-situ direct measurement of Cl. However, the large kinetic isotope effect of Cl compared with OH produces a large fractionation of 13C compared with 12C in atmospheric methane. This property can be used to estimate the likely minimum size of the methane sink attributable to MBL Cl. By taking account of the mixing of MBL air into the free troposphere, we estimate that the global methane sink due to reaction with Cl atoms in the MBL could be as large as 19Tgyr-1, or about 3.3% of the total CH4 sink. However, its impact on the methane stable carbon isotope budget is large and warrants further attention.

Description: The black carbon (BC) burden of the upper troposphere and lowermost stratosphere (UTLS) is investigated with the general circulation model (GCM) ECHAM4. The special focus is the contribution of aircraft emissions to the UTLS BC loading. Previous studies on the role of aircraft emissions in the global BC cycle either neglect BC sources located at the Earth's surface or simplify the BC cycle by assuming pre-defined BC residence times. Here, the global BC cycle including emissions, transport, and removal is explicitly simulated. The BC emissions considered include surface sources as well as BC from aviation. This enables a consistent calculation of the relative contribution of aviation to the global atmospheric BC cycle. As a further extension to the previous studies, the aviation-induced perturbation of the UTLS BC particle number concentration is investigated. The uncertainties associated with the model predictions are evaluated by means of several sensitivity studies. Especially, the sensitivity of the results to different assumptions on the BC hygroscopic properties is analysed. The simulated UTLS BC concentrations are compared to in-situ observations. The simulations suggest that the large-scale contribution of aviation to the UTLS BC mass budget typically amounts to only a few percent, even in the most frequented flight regions. The aviation impact far away from these regions is negligible. The simulated aircraft contributions to the UTLS BC particle number concentration are much larger compared to the corresponding mass perturbations. The simulations suggest that aviation can cause large-scale increases in the UTLS BC particle number concentration of more than 30% in regions highly frequented by aircraft. The relative effect shows a pronounced annual variation with the largest relative aviation impact occurring during winter.

Description: In order to gain a more comprehensive picture on different mechanisms behind atmospheric particle formation, measurement results from QUEST 2-campaign are analyzed with an aid of an aerosol dynamic model. A special emphasis is laid on air ion and charged aerosol dynamics. Model simulations indicate that kinetic nucleation of ammonia and sulphuric acid together with condensation of sulphuric acid and low-volatile organic vapours onto clusters and particles explain basic features of particle formation events as well as ion characteristics. However, an observed excess of negative ions in the diameter range 1.5-3nm and overcharge of 3-5nm particles demonstrate that ions are also involved in particle formation. These observations can be explained by preferential condensation of sulphuric acid onto negatively charged clusters and particles and/or contribution of ion-induced nucleation on particle formation. According to model simulations, which assume that the nucleation rate is equal to the sulfuric acid collision rate, the relative contribution of ion-based particle formation seems to be smaller than kinetic nucleation of neutral clusters. Conducted model simulations also corroborate the recently-presented hypothesis according to which a large number of so-called thermodynamically stable clusters (TSCs) having a diameter between 1-3nm exist in the atmosphere. TSCs were found to grow to observable sizes only under favorable conditions, e.g. when the pre-existing particle concentration was low.

Description: 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.

Description: Ozone measurements from ozonesondes, AROTAL, DIAL, and POAM III instruments during the SOLVE-2/VINTERSOL period are composited in a time-varying, flow-following quasi-conservative (PV-θ) coordinate space; the resulting composites from each instrument are mapped onto the other instruments' locations and times. The mapped data are then used to intercompare data from the different instruments. Overall, the four ozone data sets are found to be in good agreement. AROTAL shows somewhat lower values below 16 km, and DIAL has a positive bias at the upper limits of its altitude range. These intercomparisons are consistent with those obtained from more conventional near-coincident profiles, where available. Although the PV-θ mapping technique entails larger uncertainties of individual profile differences compared to direct near-coincident comparisons, the ability to include much larger numbers of comparisons can make this technique advantageous.

Description: The one-year (2001) record of aerosol data from the space borne Moderate Resolution Imaging Spectroradiometer (MODIS) is analyzed focusing on the Mediterranean region. The MODIS aerosol optical thickness standard product (AOT at 550nm) provided over both land and ocean is employed to evaluate the seasonal and spatial variability of the atmospheric particulate over the region. Expected accuracy of the MODIS AOT is (±0.05±0.2xAOT) over land and (±0.03±0.05xAOT) over ocean. The seasonal analysis reveals a significant AOT variability all over the region, with minimum values in Winter (AOT0.2). The spatial variability is also found to be considerable, particularly over land. The impact of some major urban sites and industrialized areas is detectable. For the sole Mediterranean basin, a method (aerosol mask) was implemented to separate the contribution of maritime, continental and desert dust aerosol to the total AOT. Input of both continental and desert dust particles is well captured, showing North-to-South and South-to-North AOT gradients, respectively. A quantitative summary of the AOT seasonal and regional variability is given for different sectors of the Mediterranean basin. Results of this summary were also used to test the aerosol mask assumptions and indicate the method adopted to be suitable for the aerosol type selection. Estimates of the atmospheric aerosol mass load were performed employing specifically-derived mass-to-extinction efficiencies (α). For each aerosol type, a reliable mean α value was determined on the basis of both lidar measurements of extinction and aerosol models. These estimates indicate a total of 43Mtons of desert dust suspended over the basin during 2001. A comparable value is derived for maritime aerosol. Opposite to the dust case, a minor seasonal variability (within 15%) of maritime aerosol mass is found. This latter result is considered a further check of the suitability of the methodology adopted to separate, on the basis of MODIS data, the three aerosol types which dominate the Mediterranean region.

Description: This paper presents three-dimensional prognostic O3 simulations with parameterized gas-phase photochemistry from the new NOGAPS-ALPHA middle atmosphere forecast model. We compare 5-day NOGAPS-ALPHA hindcasts of stratospheric O3 with satellite and DC-8 aircraft measurements for two cases during the SOLVE II campaign: (1) the cold, isolated vortex during 11-16 January 2003; and (2) the rapidly developing stratospheric warming of 17-22 January 2003. In the first case we test three different photochemistry parameterizations. NOGAPS-ALPHA O3 simulations using the NRL-CHEM2D parameterization give the best agreement with SAGE III and POAM III profile measurements. 5-day NOGAPS-ALPHA hindcasts of polar O3 initialized with the NASA GEOS4 analyses produce better agreement with observations than do the operational ECMWF O3 forecasts of case 1. For case 2, both NOGAPS-ALPHA and ECMWF 114-h forecasts of the split vortex structure in lower stratospheric O3 on 21 January 2003 show comparable skill. Updated ECMWF O3 forecasts of this event at hour 42 display marked improvement from the 114-h forecast; corresponding updated 42-hour NOGAPS-ALPHA prognostic O3 fields initialized with the GEOS4 analyses do not improve significantly. When NOGAPS-ALPHA prognostic O3 is initialized with the higher resolution ECMWF O3 analyses, the NOGAPS-ALPHA 42-hour lower stratospheric O3 fields closely match the operational 42-hour ECMWF O3 forecast of the 21 January event. We find that stratospheric O3 forecasts at high latitudes in winter can depend on both model initial conditions and the treatment of photochemistry over periods of 1-5 days. Overall, these results show that the new O3 initialization, photochemistry parameterization, and spectral transport in the NOGAPS-ALPHA NWP model can provide reliable short-range stratospheric O3 forecasts during Arctic winter.

Description: This paper presents a state-of-the-art gas-phase mechanism for the degradation of α-pinene by OH and its validation by box model simulations of laboratory measurements. It is based on the near-explicit mechanisms for the oxidation of α-pinene and pinonaldehyde by OH proposed by Peeters and co-workers. The extensive set of α-pinene photooxidation experiments performed in presence as well as in absence of NO by Nozière et al. (1999a) is used to test the mechanism. The comparison of the calculated vs measured concentrations as a function of time shows that the levels of OH, NO, NO2 and light are well reproduced in the model. Noting the large scatter in the experimental results as well as the difficulty to retrieve true product yields from concentrations data, a methodology is proposed for comparing the model and the data. The model succeeds in reproducing the average apparent yields of pinonaldehyde, acetone, total nitrates and total PANs in the experiments performed in presence of NO. In absence of NO, pinonaldehyde is fairly well reproduced, but acetone is largely underestimated. The dependence of the product yields on the concentration of NO and α-pinene is investigated, with a special attention on the influence of the multiple competitions of reactions affecting the peroxy radicals in the mechanism. We show that the main oxidation channels differ largely according to photochemical conditions. E.g. the pinonaldehyde yield is estimated to be about 10% in the remote atmosphere and up to 60% in very polluted areas. We stress the need for additional theoretical/laboratory work to unravel the chemistry of the primary products as well as the ozonolysis and nitrate-initiated oxidation of α-pinene.

Description: Thousands of megatons natural and anthropogenic gases are released and subsequently removed from the troposphere each year. Photochemical reactions, initiated by hydroxyl (OH) radicals, oxidise most gases to products which are more easily removed by precipitation and dry deposition at the earth's surface. Since human-induced pollution emissions strongly affect OH formation and loss, large global changes in OH concentrations are possible. Global models and observations of trace gas distributions from global networks have been used to study geographical and temporal changes in tropospheric OH. Here we present a synopsis of recent studies, indicating that global mean OH has changed remarkably little in the past century, even though regional changes have probably been substantial. Globally, depletion of OH by reactive carbon gases has been compensated by increased OH formation by nitrogen oxides, an act of "inadvertent geo-engineering". However, OH analyses for the past 1-2 decades, partly based on methyl chloroform measurements, are inconclusive. Some work, assuming that methyl chloroform emissions have largely ceased, suggests a very strong downward global OH trend in the 1990s, inconsistent with modelling studies. The discrepancy could be much reduced by assuming continued small emissions of methyl chloroform. We recommend the continuation of high precision monitoring of this compound and improved analyses based on detailed meteorological-chemical models.

Description: Boundary layer turbulence has a profound influence on the distribution of tracers with sources or sinks at the surface. The 40-year ERA-40 meteorological data set of the European Centre for Medium-range Weather Forecasts contains archived vertical diffusion coefficients. We evaluated the use of these archived diffusion coefficients versus off-line diagnosed coefficients based on other meteorological parameters archived during ERA-40 by examining the influence on the distribution of the radionuclide 222Rn in the chemistry transport model TM3. In total four different sets of vertical diffusion coefficients are compared: (i) 3-hourly vertical diffusion coefficients archived during the ERA-40 project, (ii) 3-hourly off-line diagnosed coefficients from a non-local scheme based on Holtslag and Boville (1993), Vogelezang and Holtslag (1996), and Beljaars and Viterbo (1999), (iii) 6-hourly coefficients archived during the ERA-40 project, and (iv) 6-hourly off-line diagnosed coefficients based on a local scheme described in Louis (1979) and Louis et al. (1982). The diffusion scheme to diagnose the coefficients off-line in (ii) is similar to the diffusion scheme used during the ERA-40 project (i and iii).

Description: The formation of large nitric acid trihydrate (NAT) particles has important implications for denitrification and ozone depletion. Existing theories have difficulty in explaining the formation of large NAT particles at temperatures above the ice frost point, which has been observed recently over wide Arctic regions. Our analyses reveal that high-energy comic ray particles might induce the freezing of supercooled HNO3-H2O-H2SO4 droplets when they penetrate these thermodynamically unstable droplets. The cosmic ray-induced freezing (CRIF) appears to be consistent with the observed, highly selective formation of NAT particles. We suggest a possible physical process behind the CRIF mechanism: the reorientation of polar solution molecules into the crystalline configuration in the strong electrical fields of moving secondary ions generated by passing cosmic rays. A simple formula connecting the CRIF rate to cosmic ray flux is derived with an undefined parameter constrained by observed NAT formation rates. Our simulations indicate that strong solar proton events (SPEs) may significantly enhance the formation of large NAT particles and denitrification. The CRIF mechanism offers a possible explanation for the observed high correlations between the thin nitrate-rich layers in polar ice cores and major SPEs, and the observed enhancement in the aerosol backscattering ratio at PSC layers shortly after an SPE and the significant precipitation velocity of the enhanced PSC layers. The key uncertainty in the CRIF mechanism is the probability (P) of freezing when a CR particle hits a thermodynamically, unstable STS droplet. Further studies are needed to either confirm or reject the CRIF hypothesis.

Description: The aging of soot is one of the key uncertainties in the estimation of both the direct and indirect climate effect. While freshly emitted soot is initially hydrophobic and externally mixed, it can be transferred into an internal mixture by coagulation, condensation or photochemical processes. These aging processes affect the hygroscopic qualities and hence the growth behaviour, the optical properties and eventually the lifetime of the soot particles. However, due to computational limits the aging of soot in global climate models is often only parameterised by an estimated turnover rate resulting in a lifetime of soot of several days. Hence, the aging process of soot is one of the key uncertainties governing the burden and effect of black carbon. In this study, we discuss the time scale on which diesel soot is transferred from an external to an internal mixture based on the results of our simulations with a comprehensive mesoscale model. For daytime conditions during summer condensation of sulphuric acid is dominant and the aging process occurs on a time scale of τ =8h close to the sources and τ =2h above the source region. During winter comparable time scales are found but ammonium nitrate becomes more important. During night time condensation is not effective. Then coagulation is the most important aging process and our results show time scales between 10h and 40h.

Description: Sub-micrometer atmospheric aerosol particles were studied in the Amazon region, 125 km northeast of Manaus, Brazil (-1°55.2'S, 59°28.1'W). The measurements were performed during the wet-to-dry transition period, 4-28 July 2001 as part of the LBA (Large-Scale Biosphere Atmosphere Experiment in Amazonia) CLAIRE-2001 (Cooperative LBA Airborne Regional Experiment) experiment. The number size distribution was measured with two parallel differential mobility analyzers, the hygroscopic growth at 90% RH with a Hygroscopic Tandem Mobility Analyzer (H-TDMA) and the concentrations of cloud condensation nuclei (CCN) with a cloud condensation nuclei counter. A model was developed that uses the H-TDMA data to predict the number of soluble molecules or ions in the individual particles and the corresponding minimum particle diameter for activation into a cloud droplet at a certain supersaturation. Integrating the number size distribution above this diameter, CCN concentrations were predicted with a time resolution of 10 min and compared to the measured concentrations. During the study period, three different air masses were identified and compared: clean background, air influenced by aged biomass burning, and moderately polluted air from recent local biomass burning. For the clean period 2001, similar number size distributions and hygroscopic behavior were observed as during the wet season at the same site in 1998, with mostly internally mixed particles of low diameter growth factor (~1.3 taken from dry to 90% RH). During the periods influenced by biomass burning the hygroscopic growth changed slightly, but the largest difference was seen in the number size distribution. The CCN model was found to be successful in predicting the measured CCN concentrations, typically within 25%. A sensitivity study showed relatively small dependence on the assumption of which model salt that was used to predict CCN concentrations from H-TDMA data. One strength of using H-TDMA data to predict CCN concentrations is that the model can also take into account soluble organic compounds, insofar as they go into solution at 90% RH. Another advantage is the higher time resolution compared to using size-resolved chemical composition data.

Description: Refractive and absorption indices in the UV and visible region of selected aqueous organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic dicarboxylic acids oxalic, malonic, tartronic, succinic and glutaric acid. In addition we report data for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated the aqueous organic acids at different concentrations spanning from highly diluted samples to concentrations close to saturation. The density of the investigated samples is reported and a parameterisation of the absorption and refractive index that allows the calculation of the optical constants of mixed aqueous organic acids at different concentrations is presented. The single scattering albedo is calculated for two size distributions using measured and a synthetic set of optical constants. The results show that tropospheric aerosols consisting of only these organic acids and water have a pure scattering effect.

Description: Following recent observations of molecular iodine (I2) in the coastal marine boundary layer (MBL) (Saiz-Lopez and Plane, 2004), it has become important to determine the absolute absorption cross-section of I2 at reasonably high resolution, and also to evaluate the rate of photolysis of the molecule in the lower atmosphere. The absolute absorption cross-section (σ) of gaseous I2 at room temperature and pressure (295K, 760Torr) was therefore measured between 182 and 750nm using a Fourier Transform spectrometer at a resolution of 4cm-1 (0.1nm at λ=500nm). The maximum absorption cross-section in the visible region was observed at λ=533.0nm to be σ=(4.24±0.50)x10-18cm2molecule-1. The spectrum is available as supplementary material accompanying this paper. The photo-dissociation rate constant (J) of gaseous I2 was also measured directly in a solar simulator, yielding J(I2)=0.12±0.03s-1 for the lower troposphere. This is in excellent agreement with the value of 0.12±0.015s-1 calculated using the measured absorption cross-section, terrestrial solar flux for clear sky conditions and assuming a photo-dissociation yield of unity. A two-stream radiation transfer model was then used to determine the variation in photolysis rate with solar zenith angle (SZA), from which an analytic expression is derived for use in atmospheric models. Photolysis appears to be the dominant loss process for I2 during daytime, and hence an important source of iodine atoms in the lower atmosphere.

Description: A unique halocarbon dataset has been obtained using the Australian high altitude research aircraft, the Grob G520T Egrett, during May-June 2000 with GC instrument (DIRAC), which has been previously deployed on balloon platforms. The halocarbon data generally shows a good anticorrelation with ozone data obtained simultaneously from commercial sensors. On 5 June 2000, at 380K, the Egrett entered a high latitude tongue of air over the U.K. CFC-11 and O3 data obtained on the flight show evidence of this feature. The dataset has been used, in conjunction with a 3D chemical transport model, to infer ozone depletion encountered in the midlatitude lower stratosphere during the flight. We calculate that ozone is depleted by 20% relative to its winter value in the higher latitude airmass. A suite of ozone loss tracers in the model have been used to track ozone depletion according to location relative to the vortex and chemical cycle responsible. The model, initialised on 9 December, indicates that 50% of the total chemical ozone destruction encountered in June in the middle latitudes occurred in the 90-70°N equivalent latitude band and that 70% was due to halogen chemistry.

Description: The kinetics of uptake of gaseous N2O5 on submicron aerosols containing NaCl and natural sea salt have been investigated in a flow reactor as a function of relative humidity (RH) in the range 30-80% at 295±2K and a total pressure of 1bar. The measured uptake coefficients, γ, were larger on the aerosols containing sea salt compared to those of pure NaCl, and in both cases increased with increasing RH. These observations are explained in terms of the variation in the size of the salt droplets, which leads to a limitation in the uptake rate into small particles. After correction for this effect the uptake coefficients are independent of relative humidity, and agree with those measured previously on larger droplets. A value of γ=0.025 is recommended for the reactive uptake coefficient for N2O5 on deliquesced sea salt droplets at 298K and RH〉40%.

Description: From high latitude lidar observations, quite precise information is extracted about the temporal evolution and vertical distribution of volcanic aerosol in the high latitude lower stratosphere following the eruption of Mount Pinatubo. Irreversible mixing of lower stratospheric aerosol, to the arctic pole during early 1992, is demonstrated, as a function of potential temperature and time. This work complements previous studies, which either identify vortex intrusions - without demonstrating irreversible transport, or use lower resolution satellite observations. The observed transport is associated tentatively with the vortex disturbance during late January, 1992. A very large number of high resolution lidar observations of Mount Pinatubo aerosol are analysed, without any data averaging. Averaging in measurement or analysis can cause tracer mixing to be overestimated. Averaging in the analysis can also require assumptions about which quantity has the dominant error (in this case, the equivalent latitude coordinate or the measurement), and which part of the data contains real structure. The method below attempts to avoid such assumptions.

Description: We report on measurements of the rate of homogeneous ice nucleation in supercooled water microdroplets levitated in an electrodynamic balance. By comparison of the freezing probability for droplets of radius 49µm and 19µm, we are able to conclude that homogeneous freezing is a volume-proportional process and that surface nucleation might only be important, if at all, for much smaller droplets.

Description: The aim of this paper is to compare two different modelling systems and to evaluate their ability to simulate high values of ozone concentration in typical summer episodes which take place in the north of Spain near the metropolitan area of Barcelona. As the focus of the paper is the comparison of the two systems, we do not attempt to improve the agreement by adjusting the emission inventory or model parameters. The first model, or forecasting system, is made up of three modules. The first module is a mesoscale model (MASS). This provides the initial condition for the second module, which is a nonlocal boundary layer model based on the transilient turbulence scheme. The third module is a photochemical box model (OZIPR), which is applied in Eulerian and Lagrangian modes and receives suitable information from the two previous modules. The model forecast is evaluated against ground base stations during summer 2001. The second model is the MM5/UAM-V. This is a grid model designed to predict the hourly three-dimensional ozone concentration fields. The model is applied during an ozone episode that occurred between 21 and 23 June 2001. Our results reflect the good performance of the two modelling systems when they are used in a specific episode.

Description: For the determination of photolysis rates at large zenith angles it has been demonstrated that refraction by the earth's atmosphere must be taken into account. In fact, due to the modified optical path the optical transmittance is thereby increased in most instances. Here we show that in addition the divergence of sun-rays, which is also caused by refraction but which reduces the direct solar irradiance, should not be neglected. Our calculations are based on a spherically symmetric atmosphere and include extinction by Rayleigh scattering, ozone, and background aerosol. For rays with 10km tangent altitude the divergence yields a reduction of about 10% to 40% at solar zenith angles of 91° to 96°. Moreover, we find that the divergence effect can completely cancel the relative enhancement caused by the increase of transmittance.

Description: Limited resolution in chemistry transport models (CTMs) is necessarily associated with systematic errors in the calculated chemistry, due to the artificial mixing of species on the scale of the model grid (grid-averaging). Here, the errors in calculated hydroxyl radical (OH) concentrations and ozone production rates 3 are investigated quantitatively using both direct observations and model results. Photochemical steady-state models of radical chemistry are exploited in each case to examine the effect on both OH and 3 of averaging relatively long-lived precursor species, such as O3, NOx, CO, H2O, etc. over different spatial scales. Changes in modelled 3 are estimated, independently of other model errors, by calculating the systematic effect of spatial averaging on the ozone production efficiency 1, defined as the ratio of ozone molecules produced per NOx molecule destroyed. Firstly, an investigation of in-flight measurements suggests that, at least in the northern midlatitude upper-troposphere/lower stratosphere, averaging precursor species on the scale of a T42 grid (2.75° x 2.75°) leads to a 15-20% increase in OH concentrations and a 5-10% increase in 1. Secondly, results from CTM model experiments are compared at different horizontal resolutions. Low resolution experiments are found to have significantly higher [OH] and 3 compared with high resolution experiments. The extent to which these differences may be explained by the systematic error in the model chemistry associated with grid size is estimated by degrading the high resolution data onto a low resolution grid and then recalculating 1 and [OH]. The change in calculated 1 is found to be significant and can account for much of the difference in 3 between the high and low resolution experiments. The calculated change in [OH] is less than the difference in [OH] found between the experiments, although the shortfall is likely to be due to the indirect effect of the change in modelled NOx, which is not accounted for in the calculation. It is argued that systematic errors caused by limited resolution need to be considered when evaluating the relative impacts of different pollutant sources on tropospheric ozone.

Description: In the present paper, we have calculated the outgoing longwave radiation at the top of the atmosphere (OLR at TOA) using a deterministic radiation transfer model, cloud data from ISCCP-D, and atmospheric temperature and humidity data from NCEP/NCAR reanalysis, for the seventeen-year period 1984-2000. We constructed anomaly time-series of the OLR at TOA, as well as of all of the key input climatological data, averaged in the tropical region between 20°N and 20°S. We compared the anomaly time-series of the model calculated OLR at TOA with that obtained from the ERBE S-10N (WFOV NF edition 2) non-scanner measurements. The model results display very similar seasonal and inter-annual variability as the ERBS data, and indicate a decadal increase of OLR at TOA of 1.9±0.2Wm-2/decade, which is lower than that displayed by the ERBS time-series (3.5±0.3Wm-2). Analysis of the inter-annual and long-term variability of the various parameters determining the OLR at TOA, showed that the most important contribution to the observed trend comes from a decrease in high-level cloud cover over the period 1984-2000, followed by an apparent drying of the upper troposphere and a decrease in low-level cloudiness. Opposite but small trends are introduced by a decrease in low-level cloud top pressure, an apparent cooling of the lower stratosphere (at the 50mbar level) and a small decadal increase in mid-level cloud cover.

Description: The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels.

Description: This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

Description: We present airborne in-situ trace gas measurements which were performed on eight campaigns between November 2001 and July 2003 during the SPURT-project (SPURenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region). The measurements on a quasi regular basis allowed an overview of the seasonal variations of the trace gas distribution in the tropopause region over Europe from 35°-75°N to investigate the influence of transport and mixing across the extratropical tropopause on the lowermost stratosphere. From the correlation of CO and O3 irreversible mixing of tropospheric air into the lowermost stratosphere is identified. The CO distribution indicates that transport and subsequent mixing of tropospheric air across the extratropical tropopause predominantly affects a layer, which closely follows the shape of the local tropopause. In addition, the seasonal cycle of CO2 illustrates the strong coupling of that layer to the extratropical troposphere. Both, horizontal gradients of CO on isentropes as well as the CO-O3-distribution in the lowermost stratosphere reveal that the influence of quasi-horizontal transport and subsequent mixing weakens with distance from the local tropopause. The mixing layer extends to about 25 K in potential temperature above the local tropopause exhibiting only a weak seasonality. However, at large distances from the tropopause a significant influence of tropospheric air is still evident. The relation between N2O and CO2 indicates that a significant contribution of air originating from the tropical tropopause contributes to the background air in the extratropical lowermost stratosphere.

Description: The uptake kinetics of gaseous ClONO2 and BrONO2 on aqueous surfaces were measured, as a function of temperature and liquid composition (pure water and NaCl or NaBr containing solutions) using the droplet train technique coupled to a mass spectrometer. The uptake kinetics are driven by the reactivity of these gases and, for both compounds, the uptake rates on pure water or on NaCl solutions (0.1M) are comparable. The uptake coefficient γ of ClONO2 does not depend on the temperature while that of BrONO2 increases slightly when the temperature is raised from 272 to 280K. For ClONO2 and BrONO2, the uptake rates increase on NaBr-doped droplets, enabling the estimation of the mass accommodation coefficient α. The corresponding values for α are 0.108±0.033 for ClONO2 and 0.063±0.021 for BrONO2 where the statistical errors correspond to ±2σ. The reactions of ClONO2 and BrONO2 on NaCl solutions lead respectively to the formation of Cl2 and BrCl. The uptake of ClONO2 on NaBr solutions generates BrCl as primary product, which in turn can react with NaBr to produce Br2. As expected, the only product of BrONO2 reaction on NaBr solution is Br2.

Description: This paper presents a procedure for performing and optimizing inversions for DOAS tomography and its application to measurement data. DOAS tomography is a new technique to determine 2- and 3-dimensional concentration fields of air pollutants or other trace gases by combining differential optical absorption spectroscopy (DOAS) with tomographic inversion techniques. Due to the limited amount of measured data, the resulting concentration fields are sensitive to the inversion process. Therefore detailed error estimations are needed to determine the quality of the reconstruction. In this paper we compare different row acting methods for the inversion, present a procedure for optimizing the parameters of the reconstruction process and propose a way to estimate the error-fields by numerical studies. The procedure was applied to data from the motorway emission campaign BAB II. Two dimensional NO2 cross sections at right angles to the motorway could be reconstructed qualitatively well at different meteorological situations. Additionally we present error fields for the reconstructions which show the problems and skills of the used measurement setup. Numerical studies on an improved setup for future motorway campaigns show, that DOAS tomography is able to produce high quality concentration maps.

Description: In May 2003, severe forest fires in southeast Russia resulted in smoke plumes extending widely across the Northern Hemisphere. This study combines satellite data from a variety of platforms (Moderate Resolution Imaging Spectroradiometer (MODIS), Sea-viewing Wide Field-of-view Sensor (SeaWiFS), Earth Probe Total Ozone Mapping Spectrometer (TOMS) and Global Ozone Monitoring Experiment (GOME)) and vertical aerosol profiles derived with Raman lidar measurements with results from a Lagrangian particle dispersion model to understand the transport processes that led to the large haze plumes observed over North America and Europe. The satellite images provided a unique opportunity for validating model simulations of tropospheric transport on a truly hemispheric scale. Transport of the smoke occurred in two directions: Smoke travelling northwestwards towards Scandinavia was lifted over the Urals and arrived over the Norwegian Sea. Smoke travelling eastwards to the Okhotsk Sea was also lifted, it then crossed the Bering Sea to Alaska from where it proceeded to Canada and was later even observed over Scandinavia and Eastern Europe on its way back to Russia. Not many events of this kind, if any, have been observed, documented and simulated with a transport model comprehensively. The total transport time was about 17 days. We compared transport model simulations using meteorological analysis data from both the European Centre for Medium-Range Weather Forecast (ECMWF) and the National Center for Environmental Prediction (NCEP) in order to find out how well this event could be simulated using these two datasets. Although differences between the two simulations are found on small scales, both agree remarkably well with each other and with the observations on large scales. On the basis of the available observations, it cannot be decided which simulation was more realistic.

Description: A thermal volatility technique is used to provide indirect information about the chemical composition of the aerosol involved in cirrus cloud formation. The fraction of particles that disappears after being heated to 125°C is termed volatile and the fraction that disappears between 125 and 250°C is termed semi-volatile. Particles that still remain after being heated to 250°C make up the non-volatile fraction. The thermal composition of residual particles remaining from evaporated cirrus crystals is presented and compared to interstitial aerosol particles (non-activated particles in between the cirrus crystals) for two temperature regimes (cold: T〈 -38°C, warm: -38≤T〈 -23°C), based on in-situ observations. The observations were conducted in cirrus clouds in the Southern Hemisphere (SH) and Northern Hemisphere (NH) midlatitudes during the INCA project. In the cold temperature regime, the non-volatile fraction of the residual particles was typically in the range 10 to 30% in the NH and 30 to 40% in the SH. In the warm temperature regime, the non-volatile residual fraction was typically 10 to 30% (NH) and 20 to 40% (SH). At high crystal number densities the non-volatile fraction in both temperature regimes was even higher: in the range of 30 to 40% (NH) and 40 to 50% (SH). The semi-volatile fraction was typically less than 10% in both hemispheres, causing the volatile fraction to essentially be a complement to the non-volatile fraction. In terms of the fractioning into the three types of particles, the SH cold case is clearly different compared to the other three cases (the two warm cases and the cold NH case), which share many features. In the NH data the distribution of different particle types does not seem to be temperature dependent. In all the cases, the non-volatile fraction is enriched in the residual particles compared to the fractions observed for the interstitial particles. This enrichment corresponds to about 15 (NH) and 30 (SH) percent units in the two cold cases and to 15-25 (NH) and 25-35 (SH) percent units in the two warm cases. In the NH cold case, there is a clear relation between the fractions observed in the interstitial particles and what is observed in the residual particles. The observed large fractions of non-volatile particles show that particles forming ice crystals are not entirely made up of water-soluble sulfate particles.

Description: Meteors are an important source for (a) the metal atoms of the upper atmosphere metal layers and (b) for condensation nuclei, the existence of which are a prerequisite for the formation of noctilucent cloud particles in the polar mesopause region. For a better understanding of these phenomena, it would be helpful to know accurately the annual and diurnal variations of meteor rates. So far, these rates have been little studied at polar latitudes. Therefore we have used the 33 MHz meteor radar of the ALOMAR observatory at 69° N to measure the meteor rates at this location for two full annual cycles. This site, being within 3° of the Arctic circle, offers in addition an interesting capability: The axis of its antenna field points (almost) towards the North ecliptic pole once each day of the year. In this particular viewing direction, the radar monitors the meteoroid influx from (almost) the entire ecliptic Northern hemisphere. We report on the observed diurnal variations (averaged over one month) of meteor rates and their significant alterations throughout the year. The ratio of maximum over minimum meteor rates throughout one diurnal cycle is in January and February about 5, from April through December 2.3±0.3. If compared with similar measurements at mid-latitudes, our expectation, that the amplitude of the diurnal variation is to decrease towards the North pole, is not really borne out. Observations with the antenna axis pointing towards the North ecliptic pole showed that the rate of deposition of meteoric dust is substantially larger during the Arctic NLC season than the annual mean deposition rate. The daylight meteor showers of the Arietids, Zeta Perseids, and Beta Taurids supposedly contribute considerably to the June maximum of meteor rates. We note, though, that with the radar antenna pointing as described above, all three meteor radiants are close to the local horizon but all three radiants were detected.

Description: Continuous measurements of concentrations of reactive gases, radiation, and meteorological parameters are carried out at the Meteorological Observatory Hohenpeissenberg (MOHp) as part of the Global Atmosphere Watch (GAW) Program. NO, NO2, O3 and JNO2 data from a four-year period (March 1999-December 2002) are evaluated for consistency with photochemical steady state (PSS, Φ=1) conditions. The extent of deviation from PSS reveals a strong dependence on wind direction at the station. Median values of Φ in the south sector are in the range of 2.5-5.7 and show a high variability. In contrast, values for the other directions show a relatively low variability around a median level of 2. When taking into account peroxy radical concentrations (Φext=1) PSS was reached in 13-32% of all cases for the years 1999-2002. The differences in wind sectors can be explained by local effects. It is shown that the height of the sample inlet line, its distance to the forest and the surrounding topography has a strong impact on both the absolute and relative deviations from PSS. Global irradiance and thus, photolysis of NO2 is reduced within the dense forest. Since the reaction of NO with O3 is still proceeding under these conditions, increased NO2/NO ratios are produced locally in air which is transported through the forest and advected to the MOHp site. Estimates of the peroxy radical concentration (RO2) inferred from PSS are compared with peroxy radical measurements made at the site in June 2000 during a three-week campaign. The PSS derived RO2 levels were higher than corresponding measured levels by at least a factor of 2-3. This analysis was made for a wind sector with minimal local effects on PSS. Thus the corresponding Φ median of 2 can be regarded as an upper limit for a deviation from PSS due to chemical reactions, i.e. by peroxy radicals and possible other oxidants converting additional NO to NO2.

Description: Cloud single scattering properties are mainly determined by the effective radius of the droplet size distribution. There are only few exceptions where the shape of the size distribution affects the optical properties, in particular the rainbow and the glory directions of the scattering phase function. Using observations by the Compact Airborne Spectrographic Imager (CASI) in 180° backscatter geometry, we found that high angular resolution aircraft observations of the glory provide unique new information which is not available from traditional remote sensing techniques: Using only one single wavelength, 753nm, we were able to determine not only optical thickness and effective radius, but also the width of the size distribution at cloud top. Applying this novel technique to the ACE-2 CLOUDYCOLUMN experiment, we found that the size distributions were much narrower than usually assumed in radiation calculations which is in agreement with in-situ observations during this campaign. While the shape of the size distribution has only little relevance for the radiative properties of clouds, it is extremely important for understanding their formation and evolution.

Description: Its location in the Mediterranean region and its physical characteristics render Mt. Cimone (44°11′ N, 10°42′ E), the highest peak of the Italian northern Apennines (2165 m asl), particularly suitable to study the transport of air masses from the north African desert area to Europe. During these northward transports 12 dust events were registered in measurements of the aerosol concentration at the station during the period June–December 2000, allowing the study of the impact of mineral dust transports on free tropospheric ozone concentrations, which were also measured at Mt. Cimone. Three-dimensional backward trajectories were used to determine the air mass origin, while TOMS Aerosol Index data for the Mt. Cimone area were used to confirm the presence of absorbing aerosol over the measurement site. A trajectory statistical analysis allowed identifying the main source areas of ozone and aerosols. The analysis of these back trajectories showed that central Europe and north and central Italy are the major pollution source areas for ozone and fine aerosol, whereas the north African desert regions were the most important source areas for coarse aerosol and low ozone concentrations. During dust events, the Mt. Cimone mean volume concentration for coarse particles was 6.18 µm3/cm3 compared to 0.63 µm3/cm3 in dust-free conditions, while the ozone concentrations were 4% to 21% lower than the monthly mean background values. Our observations show that surface ozone concentrations were lower than the background values in air masses coming from north Africa, and when these air masses were also rich in coarse particles, the lowest ozone values were registered. Moreover, preliminary results on the possible impact of the dust events on PM10 and ozone values measured in Italian urban and rural areas showed that during the greater number of the considered dust events, significant PM10 increases and ozone decreases have occurred in the Po valley.

Description: Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-TOF/MS). Over 10000 individual organic components were isolated from around 10µg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.

Description: Alpine valleys represent some of the most important crossroads for international heavy-duty traffic in Europe, but the full impact of this traffic on air quality is not known due to a lack of data concerning these complex systems. As part of the program "Pollution des Vallées Alpines" (POVA), we performed two sampling surveys of polycyclic aromatic hydrocarbons (PAHs) in two sensitive valleys: the Chamonix and Maurienne Valleys, between France and Italy. Sampling campaigns were performed during the summer of 2000 and the winter of 2001, with both periods taking place during the closure of the "Tunnel du Mont-Blanc". The first objective of this paper is to describe the relations between PAH concentrations, external parameters (sampling site localization, meteorological parameters, sources), and aerosol characteristics, including its carbonaceous fraction (OC and EC). The second objective is to study the capacity of PAH profiles to accurately distinguish the different emission sources. Temporal evolution of the relative concentration of an individual PAH (CHR) and the PAH groups BghiP+COR and BbF+BkF is studied in order to differentiate wood combustion, gasoline, and diesel emissions, respectively. The results show that the total particulate PAH concentrations were higher in the Chamonix valley during both seasons, despite the cessation of international traffic. Seasonal cycles, with higher concentrations in winter, are also stronger in this valley. During winter, particulate PAH concentration can reach very high levels (up to 155 ng.m-3) in this valley during cold anticyclonic periods. The examination of sources shows the impact during summer of heavy-duty traffic in the Maurienne valley and of gasoline vehicles in the Chamonix valley. During winter, Chamonix is characterized by the strong influence of wood combustion in residential fireplaces, even if the temporal evolution of specific PAH ratios are difficult to interpret. Information on sources given by PAH profiles can only be considered in qualitative terms.

Description: This is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS) - malonic acid (MA) - water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA) of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25

Description: The Danish Eulerian Hemispheric Model (DEHM) is a 3-D dynamical atmospheric transport model originally developed to describe the atmospheric transport of sulphur into the Arctic. A new version of the model, DEHM-POP, developed to study the atmospheric transport and environmental fate of persistent organic pollutants (POPs) is presented. During environmental cycling, POPs can be deposited and re-emitted several times before reaching a final destination. A description of the exchange processes between the land/ocean surfaces and the atmosphere is included in the model to account for this multi-hop transport. The α-isomer of the pesticide hexachlorocyclohexane (α-HCH) is used as tracer in the model development. The structure of the model and processes included are described in detail. The results from a model simulation showing the atmospheric transport for the years 1991 to 1998 are presented and evaluated against measurements. The annual averaged atmospheric concentration of α-HCH for the 1990s is well described by the model; however, the shorter-term average concentration for most of the stations is not well captured. This indicates that the present simple surface description needs to be refined to get a better description of the air-surface exchange processes of POPs.

Description: Recent studies show that surface ozone levels at rural sites in Greece are generally high when compared with rural ozone measurements at northern European sites. The area of SE Europe, including Greece, is not very well monitored regarding rural ozone in comparison to central and northern Europe. In order to have the best possible picture of the rural surface ozone climatology in the area, based on the available data-sets of long-term continuous monitoring stations, the 10-year measurement records (1987-1996) of the Athens peripheral station of Liossia, (12 km N of the city center) and the urban background station of Geoponiki (3 km W) as well as the 4-year record (1996-1999) of the rural station of Aliartos (100 km NW of Athens), are analyzed in this paper. The data for Liossia and Geoponiki stations are screened for cases of strong airflow from rural areas (N-NE winds stronger than 5 m/s). The variation characteristics of the average rural ozone afternoon levels (12:00-18:00), with the best vertical atmospheric mixing, are mainly examined since these measurements are expected to be representative of the broader area. In all three stations there is a characteristic seasonal variation of rural ozone concentrations with lowest winter afternoon values at about 50 μg/m3 in December-January and average summer afternoon values at about 120 μg/m3 in July-August, indicating that high summer values are observed all over the area. The rural summer afternoon ozone values are very well correlated between the three stations, implying spatial homogeneity all over the area but also temporal homogeneity, since during the 13-year period 1987-1999 the rural afternoon ozone levels remained almost constant around the value of 120 μg/m3.

Description: Ozone profiles from balloon soundings as well as SAGEII ozone profiles were used to detect anomalous large ozone concentrations of ozone in the lower stratosphere. These secondary ozone maxima are found to be the result of differential advection of ozone-poor and ozone-rich air associated with Rossby wave breaking events. The frequency and intensity of secondary ozone maxima and their geographical distribution is presented. The occurrence and amplitude of ozone secondary maxima is connected to ozone variability and trend at Uccle and account for a large part of the total ozone and lower stratospheric ozone variability.

Description: The day-long observation of a polar stratospheric cloud (PSC) by two co-located ground-based lidars at the Swedish research facility Esrange (67.9° N, 21.1° E) on 16 January 1997 is analyzed in terms of PSC dynamics and microphysics. Mesoscale modeling is utilized to simulate the meteorological setting of the lidar measurements. Microphysical properties of the PSC particles are retrieved by comparing the measured particle depolarization ratio and the PSC-averaged lidar ratio with theoretical optical data derived for different particle shapes. In the morning, nitric acid trihydrate (NAT) particles and then increasingly coexisting liquid ternary aerosol (LTA) were detected as outflow from a mountain wave-induced ice PSC upwind Esrange. The NAT PSC is in good agreement with simulations for irregular-shaped particles with length-to-diameter ratios between 0.75 and 1.25, maximum dimensions from 0.7 to 0.9 µm, and a number density from 8 to 12 cm-3 and the coexisting LTA droplets had diameters from 0.7 to 0.9 µm, a refractive index of 1.39 and a number density from 7 to 11 cm-3. The total amount of condensed HNO3 was in the range of 8–12 ppbv. The data provide further observational evidence that NAT forms via deposition nucleation on ice particles as a number of recently published papers suggest. By early afternoon the mountain-wave ice PSC expanded above the lidar site. Its optical data indicate a decrease in minimum particle size from 3 to 1.9 µm with time. Later on, following the weakening of the mountain wave, wave-induced LTA was observed only. Our study demonstrates that ground-based lidar measurements of PSCs can be comprehensively interpreted if combined with mesoscale meteorological data.

Description: The age of firn air in Antarctica at pore close-off depth is only known for a few specific sites where firn air has been sampled for analyses. We present a model that calculates the age of firn air at pore close-off depth for the entire Antarctic continent. The model basically uses four meteorological parameters as input (surface temperature, pressure, accumulation rate and wind speed). Using parameterisations for surface snow density, pore close-off density and tortuosity, in combination with a density-depth model and data of a regional atmospheric climate model, distribution of pore close-off depth for the entire Antarctic continent is determined. The deepest pore close-off depth was found for the East Antarctic Plateau near 72° E, 82° S, at 150±15 m (2σ). A firn air diffusion model was applied to calculate the age of CO2 at pore close-off depth. The results predict that the oldest firn gas (CO2 age) is located between Dome Fuji, Dome Argos and Vostok at 43° E, 78° S being 148±23 (1σ or 38 for 2σ) years old. At this location an atmospheric trace gas record should be obtained. In this study we show that methyl chloride could be recorded with a predicted length of 125 years as an example for trace gas records at this location. The longest record currently available from firn air is derived at South Pole, being 80 years. Sensitivity tests reveal that the locations with old firn air (East Antarctic Plateau) have an estimated uncertainty (2σ) for the modelled CO2 age at pore close-off depth of 30% and of about 40% for locations with younger firn air (CO2 age typically 40 years). Comparing the modelled age of CO2 at pore close-off depth with directly determined ages at seven sites yielded a correlation coefficient of 0.90 and a slope close to 1, suggesting a high level of confidence for the modelled results in spite of considerable remaining uncertainties.

Description: Particle formation resulting from activation of inorganic stable clusters by a supersaturated organic vapour was investigated using a numerical model. The applied aerosol dynamic model included a detailed description of the activation process along with a treatment of the appropriate aerosol and gas-phase processes. The obtained results suggest that both gaseous sulphuric acid and organic vapours contribute to organic particle formation in continental background areas. The initial growth of freshly-nucleated clusters is driven mainly by condensation of gaseous sulphuric acid and by a lesser extent self-coagulation. After the clusters have reached sizes of around 2 nm in diameter, low-volatile organic vapours start to condense spontaneously into the clusters, thereby accelerating their growth to detectable sizes. A shortage of gaseous sulphuric acid or organic vapours limit, or suppress altogether, the particle formation, since freshly-nucleated clusters are rapidly coagulated away by pre-existing particles. The obtained modelling results were applied to explaining the observed seasonal cycle in the number of aerosol formation events in a continental forest site.

Description: The mean monthly shortwave (SW) radiation budget at the top of atmosphere (TOA) was computed on 2.5° longitude-latitude resolution for the 14-year period from 1984 to 1997, using a radiative transfer model with long-term climatological data from the International Satellite Cloud Climatology Project (ISCCP-D2) supplemented by data from the National Centers for Environmental Prediction – National Center for Atmospheric Research (NCEP-NCAR) Global Reanalysis project, and other global data bases such as TIROS Operational Vertical Sounder (TOVS) and Global Aerosol Data Set (GADS). The model radiative fluxes at TOA were validated against Earth Radiation Budget Experiment (ERBE) S4 scanner satellite data (1985–1989). The model is able to predict the seasonal and geographical variation of SW TOA fluxes. On a mean annual and global basis, the model is in very good agreement with ERBE, overestimating the outgoing SW radiation at TOA (OSR) by 0.93 Wm-2 (or by 0.92%), within the ERBE uncertainties. At pixel level, the OSR differences between model and ERBE are mostly within ±10 Wm-2, with ±5 Wm-2 over extended regions, while there exist some geographic areas with differences of up to 40 Wm-2, associated with uncertainties in cloud properties and surface albedo. The 14-year average model results give a planetary albedo equal to 29.6% and a TOA OSR flux of 101.2 Wm-2. A significant linearly decreasing trend in OSR and planetary albedo was found, equal to 2.3 Wm-2 and 0.6% (in absolute values), respectively, over the 14-year period (from January 1984 to December 1997), indicating an increasing solar planetary warming. This planetary SW radiative heating occurs in the tropical and sub-tropical areas (20° S–20° N), with clouds being the most likely cause. The computed global mean OSR anomaly ranges within ±4 Wm-2, with signals from El Niño and La Niña events or Pinatubo eruption, whereas significant negative OSR anomalies, starting from year 1992, are also detected.