In the first part of this dissertation, we study the aging of soot, a representative type of primary aerosols, in the presence of OH-initiated oxidation products of toluene. Monodisperse soot particles are introduced into an environmental chamber where toluene is oxidized by OH radicals. The variations in soot particle properties are simultaneously monitored, including particle size, mass, organic mass faction, hygroscopicity, and optical properties. The changes in particle properties are found to be largely governed by the thickness of the organic coating that is closely related to reaction time and initial reactant concentrations. Derived from particle size and mass, the effective density increases while dynamic shape factor decreases as the organic coating grows, suggesting a compaction of the soot morphology. As the organic coating grows, the particles become more hygroscopic and have enhanced light scattering and absorption. The second part discusses the potential reactions between amines and some aerosol constituents and alteration of aerosol properties. The reactions between alkylamines and ammonium sulfate/bisulfate have been studied using a low-pressure fast flow reactor coupled to a mass spectrometer at 293 K. Alkylamines react with ammonium sulfate/bisulfate to form alkylaminium sulfates, suggesting the existence of alkylaminium salts in particle phase. We have extended our study to characterize the physicochemical properties of alkylaminium sulfates. The hygroscopicity, thermostability, and density of five representative alkylaminium sulfates have been measured by an integrated aerosol analytical system. All alkylaminium sulfate aerosols show monotonic size growth when exposed to increasing relative humidity. Mixing ammonium sulfate with alkylaminium sulfates lowers the deliquescence point corresponding to ammonium sulfate. Alkylaminium sulfates are thermally comparable to or more stable than ammonium sulfate. The densities of alkylaminium sulfate particles are lower than that of ammonium sulfate. Our results suggest that the organic compounds can effectively alter the composition and properties of atmospheric aerosols, considerably influencing the impacts of aerosols on air quality, climate forcing, and human health.

Atmospheric aerosols may be emitted directly as particles (primary) or formed from gaseous precursors (secondary) from different natural and anthropogenic sources. The highly populated South and East Asia regions are currently in a phase of rapid economic growth to which high emissions of carbonaceous aerosols are coupled. This leads to generally poor air quality and a substantial impact of anthropogenic aerosols on the regional climate. However, the emissions of different carbon aerosol components are still poorly constrained. Water-soluble organic carbon (WSOC) is a large (20-80%) component of carbonaceous aerosols that can absorb solar light and enhance cloud formation, influencing both the direct and indirect climate effects of the aerosols. A novel method for carbon isotope-based studies, including source apportionment, of the WSOC component of ambient aerosols was developed and tested for recovery efficiency and the risk of contamination using both synthetic test substances and ambient aerosols (paper I). The application of this method for the source apportionment of aerosols in South and East Asia shows that fossil fuel input to WSOC is significant in both South Asia (about 17-23%) highly impacted by biomass combustion practices and in East Asia (up to 50%) dominated by fossil energy sources (papers II, III, IV). Fossil fraction in WSOC in the outflow from northern China is considerably larger than what has been measured in South Asia, Europe and USA (paper IV). A trend of enrichment in heavy stable carbon isotopes in WSOC with distance the particles have been transported from the source is observed in the South Asian region (papers II, III). Dual-isotope (Δ14C and δ13C) analysis demonstrates that WSOC is highly influenced by atmospheric aging processes. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Submitted.</p>

Secondary organic aerosols (SOA) comprise a substantial fraction of the total global aerosol budget. While laboratory studies involving smog chambers have advanced our understanding of the formation mechanisms responsible for SOA, our knowledge of the processes leading to SOA production under ambient gaseous and particulate concentrations as well as the impact these aerosol types have on climate is poorly understood. Although the majority of atmospheric aerosols scatter radiation either directly or indirectly by serving as cloud condensation nuclei, soot is thought to have a significant warming effect through absorption. Like inorganic salts, soot may undergo atmospheric transformation through the vapor condensation of non-volatile gaseous species which will alter both its chemical and physical properties. Typical smog chamber studies investigating the formation and growth of SOA as well as the soot aging process are temporally limited by the initial gaseous concentrations injected into the chamber environment. Furthermore, data interpretation from such experiments is generally restricted to the singular gaseous species under investigation. This dissertation discusses the use of a new aerosol chamber designed to study the formation and growth of SOA and soot aging under atmospherically relevant conditions. The Ambient Aerosol Chamber for Evolution Studies (AACES) was deployed at three field sites where size and hygroscopic growth factor (HGF) of ammonium sulfate seed particles was monitored over time to examine the formation and growth of SOA. Similar studies investigating the soot aging process were also conducted in Houston, TX. It is shown that during the ambient growth of ammonium sulfate seed particles, as particle size increases, hygroscopic growth factors decrease considerably resulting in a significant organic mass fraction in the particle phase concluding an experiment. Observations of soot aging show an increase in measured size, HGF, mass and single scattering albedo. Ambient growth rate comparisons with chamber growth yielded similar trends verifying the use of AACES to study aerosol aging. Based on the results from this study, it is recommended that AACES be employed in future studies involving the production and growth of SOA and soot aging under ambient conditions in order to bridge the gaps in our current scientific knowledge.

Organic aerosols represent one of the main sources of uncertainty affecting attempts to quantify anthropogenic climate change. The diverse physical and chemical properties of organic aerosols and the varied pathways involved in their formation and aging form the basis of this uncertainty, preventing extensive and accurate representation within regional and global scale models. This inability to constrain the radiative forcings produced by organic aerosols within the atmosphere consequently acts as a limitation to the wider objective of providing reliable projections of future climate. Biomass burning constitutes one of the main anthropogenic contributions to the global atmospheric organic aerosol (OA) burden, particularly in tropical regions where the potential for perturbations to the climate system is also enhanced due to higher average levels of solar irradiance. Emissions from biomass burning have been the subject of an intense research focus in recent years, involving a combination of field campaigns and laboratory studies. These experiments have aimed to improve the limited understanding of the processes involved in the evolution of biomass burning organic aerosol (BBOA) and contribute towards the development of more robust parameterisations for climate and chemical transport models. The main objective of this thesis was to use datasets acquired from several different global regions to perform a broad analysis of the BBOA fraction, with the extensive temporal and spatial scales provided by such measurements enabling investigation of a number of key uncertainties, including regional variability in emissions and the role of secondary organic aerosol (SOA) formation in aging smoke plumes. Measurements of BBOA mass concentration obtained using Aerodyne Research Inc. Aerosol Mass Spectrometers (AMS) were used to calculate characteristic ΔOA/ΔCO ratios for different environments, accounting for the effects of dilution and contrasting fire sizes to give a proportional representation of OA production. High levels of variability in average ΔOA/ΔCO were observed both between and within different regions. The scale of this variability consistently exceeded any differences between plumes of different ages, while a widespread absence of any sustained increase in ΔOA/ΔCO with aging indicates that SOA formation does not provide a net increase in OA mass. Despite this lack of OA enhancement, increasing proportions of oxygenated OA components in aged plumes highlight the chemical transformations occurring during the evolution of BBOA, and the additional influence of OA loss through evaporation or deposition. Potential drivers of variability in ΔOA/ΔCO at source, such as changes in fuel types and combustion conditions, were investigated for controlled fires carried out within a combustion chamber. These laboratory experiments revealed a number of complex relationships between BB emissions and source conditions. Although ΔOA/ΔCO was shown to be influenced by both fuel properties and transitions between flaming and smouldering combustion phases, the extent of these effects was limited, while variability between fires exceeded levels observed for ambient measurements. These findings emphasise the complexity of the BBOA lifecycle and the need to address the extensive uncertainties associated with its various constituent processes, in order to improve understanding of eventual climate impacts from biomass burning.