Typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1988. / Bibliography: leaves 147-154. / Microfilm. / xx, 154 leaves, bound ill. 29 cm

Thesis (Ph.D.)--York University, 2006. Graduate Programme in Earth and Space Science. / Typescript. Includes bibliographical references (leaves 204-216). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR29506

A direct method for source determination of atmospheric formic and acetic acid, through carbon isotopic analysis of the ambient acids and their potential sources, has been successfully developed and tested. These first carbon isotopic measurements of formic acid in the atmosphere were found to be fairly constant, regardless of location. This is consistent with a single dominating source of formic acid, with vegetation emissions being the most likely controlling source. Collection of relatively large quantities (0.3$-$3.0 mg) of the organic acids, which was necessary for carbon isotopic measurements, was effectively accomplished by a new method using calcium hydroxide-treated filters with a high-volume sampler. Samples were collected on a regular basis at Mount Lemmon, Arizona (elevation = 9200 feet A.S.L.). Atmospheric concentrations showed a well-defined seasonal pattern, with the lowest concentrations (about 0.2 ppbv) occurring in the middle of the winter, which steadily increased to a maximum of nearly 2 ppbv in the summer. The ¹³C content (δ ¹³C) of HCOOH averaged -20.9 ± 2.5 ‰ during the growing season (April-September) and -23.2 ± 3.5 ‰ during the non-growing season at Mount Lemmon. Isotopic measurements of formic acid from several other locations included two west coast marine sites (δ ¹³C range of -19.1 to -24.6 ‰), three Colorado Rocky Mountain samples averaging -23.2 ± 1.0 ‰, two from the prairie of North Dakota (-23.5 ± 1.0 ‰) and three samples collected in the urban Tucson, Arizona area (-20.8 ± 3.4 ‰). Source measurements included HCOOH emissions from two species of formicine ants (-18.8 ± 1.7 ‰), and HCOOH in automobile exhaust (-28 ‰ from leaded gasoline, and -48.6 ‰ from unleaded). Further support for a biogenic source of atmospheric HCOOH came from the carbon-14 analysis of six Mount Lemmon HCOOH samples (93-113% modern carbon), using accelerator mass spectrometry. Carbon isotopic fractionation during exchange of HCOOH between the liquid and gas phases was investigated through a gas/liquid partitioning experiment. A first experimental measurement of the Henry's Law coefficient (Kᴴ) averaged 7400 ± 800 M/atm. Fractionation between HCOOH(g) and HCOOH(aq) was found to be negligible.

M.Sc., Faculty of Science, University of the Witwatersrand, 2011 / Biogenic volatile organic compounds (BVOCs), in the presence of nitrogen oxide gases (NOx), play a role in the production of tropospheric ozone (O3) which is an effective greenhouse gas and is hazardous to human health (Haagen-Smit, 1952, Chameides et al, 1988, Atkinson, 2000, Kanakidou et al, 2004). Isoprene is a single BVOC that accounts for over 50% of all emitted BVOCs. Isoprene emissions are species specific and vary according to temperature, light and leaf area index. Climate change studies predict that the geographic distribution of species, temperature ranges, light intensity and leaf area index will shift, thus altering future isoprene emissions. Several attempts to model BVOC emissions have been undertaken in an effort to quantify BVOC emission rates and the impact on ozone formation. The most widely used and empirically tested emission algorithms to date were developed by Guenther et al (1993) and are incorporated into the emission model Model of Emissions of Gases and Aerosols from Nature (MEGAN). MEGAN is used in this study to model isoprene emission rates over southern Africa under current and future climate conditions. Current and future climate conditions are taken from the regional climate model, Conformal-Cubic Atmospheric Model (C-CAM), which has been shown to simulate current climate well for the region. Emissions were modelled for January and July only, to represent summer and winter conditions. January isoprene emission rates for the current climate range from 0 to 1.41 gm-2month-1 and total 0.938 Tg of isoprene for the study domain. The highest emission rates are caused by combinations of driving variables which are: high temperature only; high temperature and high leaf area index; high emission factor and high leaf area index. Emission rates effectively shut down in July due to low temperatures and low leaf area index. July emission rates range from 0 to 0.61 gm-2month-1 and total 0.208 Tg of isoprene. Temperature is shown to cause the greatest variation in isoprene emission rates, and thus future scenarios represent an increase in temperature only. The spatial distribution of future emission rates does not shift when compared to current emission rates, but does show an increase in magnitude. Future emission totals for January increase iv by 34% to 1.259 Tg of isoprene and the July emission total increases by 38% to 0.289 Tg of isoprene. Future emission rates responded to temperature as expected, increasing in magnitude, rate of change and range of temperature over which the greatest rate of change occurs. Three areas demonstrating the highest increase in emission rates and highest future emission rates were identified. As temperature was the only variable altered in future scenarios, these areas can be deemed as areas most sensitive to changes in temperature. These areas are situated near the Angola-Namibia border, the Northern Interior of South Africa and the low-lying areas of Mozambique.

Dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg for the Degree of Master of Science. / Recent research has highlighted the lack of information on elevated absolutely stable layers per se throughout the troposphere over the southern African subcontinent. Hence a climatology of elevated absolutely stable layers is derived for each of four predominant synoptic circulation types over Southern Africa; namely semi-permanent continental anticyclones, transient mid-latitude ridging anticyclones, westerly wave baroclinic disturbances and barotropic quasi-stationary easterly waves. The horizontal and vertical structures as well as the temporal persistence of elevated absolutely stable layers are analysed using radiosonde data from nine South African aerological stations from the period 1986-1993. In addition, a climatology is derived for the mid-winter stability maximum, during the month of July from 1989-1993, in order to gain greater insights into the influence of anticyclonic circulation on the elevated absolutely stable layers. Four non-surface stable layers are identified over the country, at approximately the 800 hPa, 700 hPa, 500 hPa and 300 hPa levels. The lower of these layer occurs only over the coastal regions. All of the discontinuities exhibit a high degree of persistence and appear to be rapidly reconstructed subsequent to synoptic scale disturbances. The presence of these layers has obvious implications for local as well as global pollution transport, since stable discontinuities trap pollutants below their bases and act as upper air boundaries. As a consequence, global-scale transport of aerosols and trace gases in the free air is controlled to a large degree by these discontinuities. Greater insights into the mechanisms controlling such large-scale transport are essential in ascertaining southern Africa's contribution to greenhouse gas concentrations. Moreover, the persistence and strength of the discontinuities have implications for rainfall over the subcontinent, with the lower layers in particular acting as a vertical boundary to turbulence and mixing, and thus hindering the development of convective precipitation. / AC 2018