This thesis focuses on the volatile and hygroscopic properties of mixed aerosol species. In particular, the influence organic species of varying solubility have upon seed aerosols. Aerosol studies were conducted at the Paul Scherrer Institut Laboratory for Atmospheric Chemistry (PSI-LAC, Villigen, Switzerland) and at the Queensland University of Technology International Laboratory for Air Quality and Health (QUT-ILAQH, Brisbane, Australia). The primary measurement tool employed in this program was the Volatilisation and Hygroscopicity Tandem Differential Mobility Analyser (VHTDMA - Johnson et al. 2004). This system was initially developed at QUT within the ILAQH and was completely re-developed as part of this project (see Section 1.4 for a description of this process). The new VHTDMA was deployed to the PSI-LAC where an analysis of the volatile and hygroscopic properties of ammonium sulphate seeds coated with organic species formed from the photo-oxidation of á-pinene was conducted. This investigation was driven by a desire to understand the influence of atmospherically prevalent organics upon water uptake by material with cloud forming capabilities. Of particular note from this campaign were observed influences of partially soluble organic coatings upon inorganic ammonium sulphate seeds above and below their deliquescence relative humidity (DRH). Above the DRH of the seed increasing the volume fraction of the organic component was shown to reduce the water uptake of the mixed particle. Below the DRH the organic was shown to activate the water uptake of the seed. This was the first time this effect had been observed for á-pinene derived SOA. In contrast with the simulated aerosols generated at the PSI-LAC a case study of the volatile and hygroscopic properties of diesel emissions was undertaken. During this stage of the project ternary nucleation was shown, for the first time, to be one of the processes involved in formation of diesel particulate matter. Furthermore, these particles were shown to be coated with a volatile hydrophobic material which prevented the water uptake of the highly hygroscopic material below. This result was a first and indicated that previous studies into the hygroscopicity of diesel emission had erroneously reported the particles to be hydrophobic. Both of these results contradict the previously upheld Zdanovksii-Stokes-Robinson (ZSR) additive rule for water uptake by mixed species. This is an important contribution as it adds to the weight of evidence that limits the validity of this rule.

<p>The uncertainty of the climate and health effects of aerosols is still large, one important reason being lack of knowledge of the primary emissions. This thesis combines laboratory and field experiments, and process modelling in an effort to better quantify the submicrometre aerosol emissions and to understand some of the processes in the atmosphere.</p><p>A parameterisation was derived for the source flux of sea salt particles (particles m^-2s^-1) in the size range 0.02-2.8 µm dry diameter (D_p), it is the first parameterisation to almost cover two full decades of the submicrometre sea salt aerosol production, and to include the effect of water temperature. This sea salt parameterisation was validated for temperate water in the 0.1-1.1 μm D_p range using in situ size resolved emissions of marine aerosol particles, which were measured with the eddy covariance (EC) method. For periods sampled air was heated to 300ºC in order to evaporate semi-volatile organics and isolate the sea salt fraction. Comparisons with the total aerosol emissions suggest that in these emissions organic carbon and sea salt are internally mixed in the same particles. Finally an aerosol dynamics model was modified for marine conditions. In the model parameterised emissions of sea salt was included together with aerosol dynamics, chemistry and clouds representative for the marine boundary layer. The sea salt emissions are together with secondary sulphate, and cloud processing able to reproduce a typical marine aerosol size distribution and cloud condensation nuclei population.</p><p>Measurements with the EC method of the road traffic related aerosol source number flux for D_p>0.011 µm show that the major part of the aerosol fluxes is due to road traffic emissions. Both an emission factor for the whole fleet mix in Stockholm (1.4x10¹⁴ vehicle^-1 km^-1) and separate emission factors for light- and heavy-duty vehicles (HDV) were deduced. The result shows that during weekdays 70-80% of the emissions come from HDV.</p>

The uncertainty of the climate and health effects of aerosols is still large, one important reason being lack of knowledge of the primary emissions. This thesis combines laboratory and field experiments, and process modelling in an effort to better quantify the submicrometre aerosol emissions and to understand some of the processes in the atmosphere. A parameterisation was derived for the source flux of sea salt particles (particles m-2 s-1) in the size range 0.02-2.8 µm dry diameter (Dp), it is the first parameterisation to almost cover two full decades of the submicrometre sea salt aerosol production, and to include the effect of water temperature. This sea salt parameterisation was validated for temperate water in the 0.1-1.1 μm Dp range using in situ size resolved emissions of marine aerosol particles, which were measured with the eddy covariance (EC) method. For periods sampled air was heated to 300ºC in order to evaporate semi-volatile organics and isolate the sea salt fraction. Comparisons with the total aerosol emissions suggest that in these emissions organic carbon and sea salt are internally mixed in the same particles. Finally an aerosol dynamics model was modified for marine conditions. In the model parameterised emissions of sea salt was included together with aerosol dynamics, chemistry and clouds representative for the marine boundary layer. The sea salt emissions are together with secondary sulphate, and cloud processing able to reproduce a typical marine aerosol size distribution and cloud condensation nuclei population. Measurements with the EC method of the road traffic related aerosol source number flux for Dp&gt;0.011 µm show that the major part of the aerosol fluxes is due to road traffic emissions. Both an emission factor for the whole fleet mix in Stockholm (1.4x1014 vehicle-1 km-1) and separate emission factors for light- and heavy-duty vehicles (HDV) were deduced. The result shows that during weekdays 70-80% of the emissions come from HDV.

Nano-particle aerosols are one of the major types of air pollutants in the urban indoor and outdoor environments. Therefore, determination of mechanisms of formation, dispersion, evolution, and transformation of combustion aerosols near the major source of this type of air pollution - busy roads and road networks - is one of the most essential and urgent goals. This Thesis addresses this particular direction of research by filling in gaps in the existing physical understanding of aerosol behaviour and evolution. The applicability of the Gaussian plume model to combustion aerosols near busy roads is discussed and used for the numerical analysis of aerosol dispersion. New methods of determination of emission factors from the average fleet on a road and from different types of vehicles are developed. Strong and fast evolution processes in combustion aerosols near busy roads are discovered experimentally, interpreted, modelled, and statistically analysed. A new major mechanism of aerosol evolution based on the intensive thermal fragmentation of nano-particles is proposed, discussed and modelled. A comprehensive interpretation of mutual transformations of particle modes, a strong maximum of the total number concentration at an optimal distance from the road, increase of the proportion of small nano-particles far from the road is suggested. Modelling of the new mechanism is developed on the basis of the theory of turbulent diffusion, kinetic equations, and theory of stochastic evaporation/degradation processes. Several new powerful statistical methods of analysis are developed for comprehensive data analysis in the presence of strong turbulent mixing and stochastic fluctuations of environmental factors and parameters. These methods are based upon the moving average approach, multi-variate and canonical correlation analyses. As a result, an important new physical insight into the relationships/interactions between particle modes, atmospheric parameters and traffic conditions is presented. In particular, a new definition of particle modes as groups of particles with similar diameters, characterised by strong mutual correlations, is introduced. Likely sources of different particle modes near a busy road are identified and investigated. Strong anti-correlations between some of the particle modes are discovered and interpreted using the derived fragmentation theorem. The results obtained in this thesis will be important for accurate prediction of aerosol pollution levels in the outdoor and indoor environments, for the reliable determination of human exposure and impact of transport emissions on the environment on local and possibly global scales. This work will also be important for the development of reliable and scientifically-based national and international standards for nano-particle emissions.