Gwaze, Patience
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Physical and chemical properties of atmospheric particles are fundamental but not necessarily easily accessible parameters. Uncertainties in these parameters are responsible for some uncertainties associated with radiative impacts of aerosol particles in global climate models. The uncertainties pertain to limitations of sampling and measurement devices, difficulties in modelling aerosols (source strengths, spatial and temporal variability) and in understanding microphysical and optical properties of aerosol particles. Physical and chemical properties can be obtained at single-particle level by microscopy analyses of individual particles. Using refined analytical and interpretative techniques to derive some of these fundamental properties, aerosol particles collected in various field campaigns and laboratory experiments were investigated using two high resolution microscopes. The particles were collected during the LBA-EUSTACH, Large-Scale Biosphere-Atmosphere Experiment part of European Studies on Trace Gases and Atmospheric Chemistry; SMOCC campaign, Smoke Aerosols, Clouds, Rainfall and Climate; CTBH II, Cape Town Brown Haze II campaign; and a controlled combustion experiment. Microscopy techniques were compared and complemented with conventional techniques to characterise particle sizes, shapes, chemical compositions and mixing states. Particle size distributions were compared between geometric equivalent sizes measured from microscopes and aerodynamic equivalent diameters, while taking into account particle densities. Large differences were found between the particle sizing techniques. Microscopy sizes (3D) were systematically lower than expected, and depended on the relative humidity during particle sampling. Differences were attributed to loss of mass, presumably water adsorbed on particles. Losses were high and could not be accounted for by known humidity growth factors suggesting losses of other volatile compounds adsorbed on particles as well. Findings suggest that there are inherent problems in defining particle sizes with different sizing techniques, despite accounting for humidity growth of particles and particle density. For collected particles, there are mass losses on individual particles, as opposed to particle losses to walls during sampling. These losses will inevitably bias observed mass distributions derived from collected particles and hence their number-size distributions. Relatively young aggregated soot particles from wood combustion were investigated for particle morphology (fractality, specific mass) and dynamic properties. Based on a procedure that has been validated on modelled aggregates, several important parameters to characterise geometry and drag-to-mass relationship of aggregates were derived. Three techniques were used to derive fractal dimension of soot aggregates. Averaged fractal dimension was found to be Df = 1.82 ± 0.08. Dynamic shape factors of soot particles were 1.7 to 2.5 and increasing with mass of aggregates. In the regime 0.2 < Kn < 0.7 (Knudsen number, Kn = 2/dmob) the mobility diameter dmob was observed to be proportional to the radius of gyration with a ratio dmob/2Rg = 0.81 ± 0.07. Specific surface area of aggregates was determined to be 70 ± 10 m2g−1 based on SEM image analysis. These parameters can be used directly in modelling microphysical behaviour of freshly formed soot particles from biomass combustion with fractal dimension of Df ≈ 1.80. Chemical composition and size distributions of particles were investigated on filter samples collected during intense winter brown haze episodes in Cape Town. The sampling technique offered the capability to characterise highly heterogeneous aerosols over a polluted urban environment. Based on morphology and elemental composition, particles were categorised into seven particle groups of: aggregated soot particles, mineral dust, sulphates (SO2− 4 ), sea-salt, tar balls/fly ash, rod-shaped particles associated with soot agglomerates and those that could not be attributed to any of these groups were labelled as ‘others’. Apportionments of chemical species were highly variable both spatially and temporally. These variations indicate lack of lateral mixing and dependence of particle chemical compositions on localised and point sources within the Cape Town area. Sulphate and aggregated soot particles were externally mixed with fractional number concentrations of 0− 82% and 11%−46%, respectively. Aerosol complex refractive indices were derived from the chemical apportionment and particle abundance determined in microscopy analyses. The refractive indices were combined with in-situ measurements of number-size distribution to determine optical properties of aerosols. Single scattering albedo, !0, varied from 0.61 to 0.94 with a mean value of 0.72±0.08. The !0 is much lower than is generally reported in literature, and this was attributed to high concentrations of highly absorbing anthropogenic soot observed in SEM analysis. The mean extinction coefficient ep was 194 ± 195 Mm−1. ep and !0 clearly demonstrated and explained quantitatively the visibility reduction due to particles in the Cape Town atmosphere, reduction observed as the brown haze phenomenon. In all the three case studies, microscopy single particle analysis played a critical role in advancing knowledge of understanding properties of aerosol particles in the atmosphere.
Student Number : 0318623R - PhD thesis - School of Geosciences - Faculty of Science
aerosol particles , size distribution , fractal , morphology , mobility , brown haze , SEM , AFM