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From molecular clusters to nanoparticles: second-generation ion-mediated nucleation model

Ions, which are generated in the atmosphere by galactic cosmic rays and other ionization sources, may play an important role in the formation of atmospheric aerosols. In the paper, a new second-generation ion-mediated nucleation (IMN) model is presented. The new model explicitly treats the evaporation of neutral and charged clusters and it describes the evolution of the size spectra and composition of both charged and neutral clusters/particles ranging from small clusters of few molecules to large particles of several micrometers in diameter. Schemes used to calculate the evaporation coefficients for small neutral and charged clusters are consistent with the experimental data within the uncertainty range. The present IMN model, which is size-, composition-, and type-resolved, is a powerful tool for investigating the dominant mechanisms and key parameters controlling the formation and subsequent growth of nanoparticles in the atmosphere. This model can be used to analyze simultaneous measurements of the ion-mobility spectra and particle size distributions, which became available only recently. General features of the spectra for ions smaller than the critical size, size-dependent fractions of charged nanoparticles, and asymmetrical charging of freshly nucleated particles predicted by the new IMN model are consistent with recent measurements. Results obtained using the second generation IMN model, in which the most recent thermodynamic data for neutral and charged H2SO4-H2O clusters were used, suggest that ion-mediated nucleation of H2SO4-H2O can lead to a significant production of new particles in the lower atmosphere (including the boundary layer) under favorable conditions. It has been shown that freshly nucleated particles of few nanometers in size can grow by the condensation of low volatile organic compounds to the size of cloud condensation nuclei. In such cases, the chemical composition of nucleated particles larger than ~10 nm is dominated by organics.
The total ozone field separated into meteorological regimes – Part II: Northern Hemisphere mid-latitude total ozone trends

Previous studies have presented clear evidence that the Northern Hemisphere total ozone field can be separated into distinct regimes (tropical, midlatitude, polar, and arctic) the boundaries of which are associated with the subtropical and polar upper troposphere fronts, and in the winter, the polar vortex. This paper presents a study of total ozone variability within these regimes, from 1979–2003, using data from the TOMS instruments. The change in ozone within each regime for the period January 1979–May 1991, a period of rapid total ozone change, was studied in detail. Previous studies had observed a zonal linear trend of −3.15% per decade for the latitude band 25°–60° N. When the ozone field is separated by regime, linear trends of −1.4%, 2.3%, and 3.0%, per decade for the tropical, midlatitude, and polar regimes, respectively, are observed. The changes in the relative areas of the regimes were also derived from the ozone data. The relative area of the polar regime decreased by about 20%; the tropical regime increased by about 10% over this period. No significant change was detected for the midlatitude regime. From the trends in the relative area and total ozone it is deduced that 35% of the trend between 25° and 60° N, from January 1979–May 1991 is due to movement of the upper troposphere fronts. The changes in the relative areas can be associated with a change in the mean latitude of the subtropical and polar fronts within the latitude interval 25° to 60° N. Over the period from January 1979 to May 1991, both fronts moved northward by 1.1±0.2 degrees per decade. Over the entire period of the study, 1979–2003, the subtropical front moved northward at a rate of 1.1±0.1 degrees per decade, while the polar front moved by 0.5±0.1 degrees per decade.
Radiative forcing by aerosols as derived from the AeroCom present-day and pre-industrial simulations

Nine different global models with detailed aerosol modules have independently produced instantaneous direct radiative forcing due to anthropogenic aerosols. The anthropogenic impact is derived from the difference of two model simulations with prescribed aerosol emissions, one for present-day and one for pre-industrial conditions. The difference in the solar energy budget at the top of the atmosphere (ToA) yields a new harmonized estimate for the aerosol direct radiative forcing (RF) under all-sky conditions. On a global annual basis RF is −0.22 Wm−2, ranging from +0.04 to −0.41 Wm−2, with a standard deviation of ±0.16 Wm−2. Anthropogenic nitrate and dust are not included in this estimate. No model shows a significant positive all-sky RF. The corresponding clear-sky RF is −0.68 Wm−2. The cloud-sky RF was derived based on all-sky and clear-sky RF and modelled cloud cover. It was significantly different from zero and ranged between −0.16 and +0.34 Wm−2. A sensitivity analysis shows that the total aerosol RF is influenced by considerable diversity in simulated residence times, mass extinction coefficients and most importantly forcing efficiencies (forcing per unit optical depth). The clear-sky forcing efficiency (forcing per unit optical depth) has diversity comparable to that for the all-sky/ clear-sky forcing ratio. While the diversity in clear-sky forcing efficiency is impacted by factors such as aerosol absorption, size, and surface albedo, we can show that the all-sky/clear-sky forcing ratio is important because all-sky forcing estimates require proper representation of cloud fields and the correct relative altitude placement between absorbing aerosol and clouds. The analysis of the sulphate RF shows that long sulphate residence times are compensated by low mass extinction coefficients and vice versa. This is explained by more sulphate particle humidity growth and thus higher extinction in those models where short-lived sulphate is present at lower altitude and vice versa. Solar atmospheric forcing within the atmospheric column is estimated at +0.82±0.17 Wm−2. The local annual average maxima of atmospheric forcing exceed +5 Wm−2 confirming the regional character of aerosol impacts on climate. The annual average surface forcing is −1.02±0.23 Wm−2. With the current uncertainties in the modelling of the radiative forcing due to the direct aerosol effect we show here that an estimate from one model is not sufficient but a combination of several model estimates is necessary to provide a mean and to explore the uncertainty.
Modeling of biomass smoke injection into the lower stratosphere by a large forest fire (Part I): reference simulation

Wildland fires in boreal regions have the potential to initiate deep convection, so-called pyro-convection, due to their release of sensible heat. Under favorable atmospheric conditions, large fires can result in pyro-convection that transports the emissions into the upper troposphere and the lower stratosphere. Here, we present three-dimensional model simulations of the injection of fire emissions into the lower stratosphere by pyro-convection. These model simulations are constrained and evaluated with observations obtained from the Chisholm fire in Alberta, Canada, in 2001. The active tracer high resolution atmospheric model (ATHAM) is initialized with observations obtained by radiosonde. Information on the fire forcing is obtained from ground-based observations of the mass and moisture of the burned fuel. Based on radar observations, the pyro-convection reached an altitude of about 13 km, well above the tropopause, which was located at about 11.2 km. The model simulation yields a similarly strong convection with an overshoot of the convection above the tropopause. The main outflow from the pyro-convection occurs at about 10.6 km, but a significant fraction (about 8%) of the emitted mass of the smoke aerosol is transported above the tropopause. In contrast to regular convection, the region with maximum updraft velocity in the pyro-convection is located close to the surface above the fire. This results in high updraft velocities >10 m s−1 at cloud base. The temperature anomaly in the plume decreases rapidly with height from values above 50 K at the fire to about 5 K at about 3000 m above the fire. While the sensible heat released from the fire is responsible for the initiation of convection in the model, the release of latent heat from condensation and freezing dominates the overall energy budget. Emissions of water vapor from the fire do not significantly contribute to the energy budget of the convection.
Modeling of biomass smoke injection into the lower stratosphere by a large forest fire (Part II): sensitivity studies

The Chisholm forest fire that burned in Alberta, Canada, in May 2001 resulted in injection of substantial amounts of smoke into the lower stratosphere. We used the cloud-resolving plume model ATHAM (Active Tracer High resolution Atmospheric Model) to investigate the importance of different contributing factors to the severe intensification of the convection induced by the Chisholm fire and the subsequent injection of biomass smoke into the lower stratosphere. The simulations show strong sensitivity of the pyro-convection to background meteorology. This explains the observed coincidence of the convective blow-up of the fire plume and the passage of a synoptic cold front. Furthermore, we performed model sensitivity studies to the rate of release of sensible heat and water vapor from the fire. The release of sensible heat by the fire plays a dominant role for the dynamic development of the pyro-cumulonimbus cloud (pyroCb) and the height to which smoke is transported. The convection is very sensitive to the heat flux from the fire. The emissions of water vapor play a less significant role for the injection height but enhance the amount of smoke transported beyond the tropopause level. The aerosol burden in the plume has a strong impact on the microphysical structure of the resulting convective cloud. The dynamic evolution of the pyroCb, however, is only weakly sensitive to the abundance of cloud condensation nuclei (CCN) from the fire. In contrast to previous findings by other studies of convective clouds, we found that fire CCN have a negative effect on the convection dynamics because they give rise to a delay in the freezing of cloud droplets. Even in a simulation without fire CCN, there is no precipitation formation within the updraft region of the pyroCb. Enhancement of convection by aerosols as reported from studies of other cases of convection is therefore not found in our study.
A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber

An Aerodyne Aerosol Mass Spectrometer (AMS) has been utilised to provide on-line measurements of the mass spectral signatures and mass size distributions of the oxidation products resulting from irradiating 1,3,5-trimethylbenzene (1,3,5-TMB) and α-pinene, separately, in the presence of nitrogen oxide, nitrogen dioxide and propene in a reaction chamber. Mass spectral results indicate that both precursors produce SOA with broadly similar chemical functionality of a highly oxidised nature. However, significant differences occur in the minor mass spectral fragments for the SOA in the two reaction systems, indicating that they have different molecular composition. Nitrogen-containing organic compounds have been observed in the photooxidation products of both precursors, and their formation appeared to be controlled by the temporal variability of NOx. Although the overall fragmentation patterns of the photooxidation products in both systems did not change substantially over the duration of each experiment, the contribution of some individual mass fragments to total mass appeared to be influenced by the irradiation time. The effective densities of the 1,3,5-TMB and α-pinene SOA particles were determined for various particle sizes using the relationship between mobility and vacuum aerodynamic diameters. The effective density for the 1,3,5-TMB SOA ranged from 1.35–1.40 g/cm3, while that for α-pinene SOA ranged from 1.29–1.32 g/cm3. The determined effective densities did not show dependence on irradiation time. Results suggest that further chemical processing of SOA takes place in the real atmosphere, as neither the α-pinene nor the 1,3,5-TMB experimental results reproduce the right relative product distribution between carbonyl-containing and multifunctional carboxylic acid species measured at ambient locations influenced by aged continental organic aerosols.
What does reflection from cloud sides tell us about vertical distribution of cloud droplet sizes?

Cloud development, the onset of precipitation and the effect of aerosol on clouds depend on the structure of the cloud profiles of droplet size and phase. Aircraft measurements of cloud profiles are limited in their temporal and spatial extent. Satellites were used to observe cloud tops not cloud profiles with vertical profiles of precipitation-sized droplets anticipated from CloudSat.  The recently proposed CLAIM-3D satellite mission (cloud aerosol interaction mission in 3-D) suggests to measure profiles of cloud microphysical properties by retrieving them from the solar and infrared radiation reflected or emitted from cloud sides. Inversion of measurements from the cloud sides requires rigorous understanding of the 3-dimentional (3-D) properties of clouds. Here we discuss the reflected sunlight from the cloud sides and top at two wavelengths: one nonabsorbing to solar radiation (0.67 μm) and one with liquid water efficient absorption of solar radiation (2.1 μm). In contrast to the plane-parallel approximation, a conventional approach to all current operational retrievals, 3-D radiative transfer is used for interpreting the observed reflectances. General properties of the radiation reflected from the sides of an isolated cloud are discussed. As a proof of concept, the paper shows a few examples of radiation reflected from cloud fields generated by a simple stochastic cloud model with the prescribed vertically resolved microphysics. To retrieve the information about droplet sizes, we propose to use the probability density function of the droplet size distribution and its first two moments instead of the assumption about fixed values of the droplet effective radius. The retrieval algorithm is based on the Bayesian theorem that combines prior information about cloud structure and microphysics with radiative transfer calculations.
Estimating a relationship between aerosol optical thickness and surface wind speed over the ocean

Retrieved aerosol optical thickness (AOT) based on data obtained by the Sea viewing Wide Field Sensor (SeaWiFS) is combined with surface wind speed, obtained at the European Centre for Medium-Range Weather Forecasts (ECMWFs), over the North Pacific for September 2001. In this study a cloud screening approach is introduced in an attempt to exclude pixels partly or fully covered by clouds. The relatively broad swath width for which the nadir looking SeaWiFS instrument scanned over the North Pacific means that the AOT can be estimated according to relatively large range of wind speeds for each of the scenes analyzed. The sensitivity in AOT due to sea salt and hygroscopic growth of the marine aerosols has also been investigated. The validation of the results is based on previous parameterization in combination with the environmental quantities wind speed, RH and boundary layer height (BLH), estimated at the ECMWF. In this study a factor of 2 higher mean AOT is obtained for a wind speed up to about 13 m s−1 for September 2001 over remote ocean areas. Furthermore, a factor of 2 higher AOT is more or less supported by the validation of the results. Approximately, 50% of the enhancement seems to be due to hygroscopic growth of the marine aerosols and the remaining part due to increase in the sea salt particle mass concentrations, caused by a wind driven water vapor and sea salt flux, respectively. Reasonable agreement occurs also between satellites retrieved aerosol optical thickness and AOT observed at several AERONET (Aerosol Robotic NETwork) ground-based remote sensing stations. Finally, possible reasons why relatively large standard deviations occur around the mean values of AOT estimated for a single scene are discussed.
Assimilation of TES CO into a global CTM: first results

We present results from the first assimilation of carbon monoxide (CO) observations from the Tropospheric Emission Spectrometer (TES) into a global three-dimensional (3-D) chemistry and transport model (CTM). A sequential sub-optimal Kalman filter assimilation scheme (Khattatov et al., 2000) was applied to assimilate TES CO profiles during November 2004 into the GEOS-Chem global 3-D CTM. The assimilation results were compared with MOPITT and MOZAIC observations. The assimilation significantly improves model simulation of CO in the middle to upper troposphere, where the MOPITT versus model bias was reduced by up to two-thirds. Assimilation results show higher levels of CO in the southern tropics, consistent with MOPITT observations. We find good agreement between the TES assimilated model estimates of CO and in situ measurements from the MOZAIC program, which shows a negative bias of up to 10 ppbv in middle and upper tropospheric TES CO. The results demonstrate how assimilation can be used for non-coincident validation of TES CO profile retrievals.
Aerosol distribution over the western Mediterranean basin during a Tramontane/Mistral event

This paper investigates experimentally and numerically the time evolution of the spatial distribution of aerosols over the Western Mediterranean basin during 24 March 1998 Mistral event documented during the FETCH experiment. Mistral and Tramontane are very frequent northerly winds (5–15 days per month) accelerated along the Rhône and Aude valley (France) that can transport natural and anthropogenic aerosols offshore as far as a few hundreds of kilometers which can in turn have an impact on the radiation budget over the Mediterranean Sea and on precipitation. The spatial distribution of aerosols was documented by means of the airborne lidar LEANDRE-2 and spaceborne radiometer SeaWIFS, and a validated mesoscale chemical simulation using the chemistry-transport model CHIMERE with an aerosol module, forced by the non-hydrostatic model MM5. This study shows that: (1) the Mistral contributes to the offshore exportation of a large amount of aerosols originally emitted over continental Europe (in particular ammonium nitrate in the particulate phase and sulfates) and along the shore from the industrialized and urban areas of Fos-Berre/Marseille. The Genoa surface low contributes to advect the aerosols along a cyclonic trajectory that skirts the North African coast and reaches Italy; (2) the aerosol concentration pattern is very unsteady as a result of the time evolution of the two winds (or Genoa cyclone position): The Tramontane wind prevails in the morning hours of 24 March, leaving room for the Mistral wind and an unusually strong Ligurian outflow in the afternoon. The wakes trailing downstream the Massif Central and the Alps prevent any horizontal diffusion of the aerosols and can, at times, contribute to aerosol stagnation.