The indirect aerosol effect contributes to major uncertainties in determining the radiation budget of the earth. A large uncertainty is due to the formation of ice clouds onto natural or anthropogenic aerosols. Field studies have shown that mineral type particles are often associated with ice crystals in the mid-upper troposphere and given the long residence time in the atmosphere of dust particles (~2 weeks in the absence of precipitation), their contribution to ice formation processes is not fully defined. In order to probe ice formation onto natural mineral dust in a setting where it could be suspended as aerosol, a new continuous flow diffusion chamber (CFDC) was built. This allowed investigations of the effects of total aerosol surface area and particle size. The CFDC was also used in an international inter-comparison of ice nucleation instrumentation to compare efficiencies of soot, biological aerosol (bacteria) and samples of natural desert dusts from different regions of the world. The laboratory observations were parameterized using nucleation rates (Jhet) and contact angles () as described by classical nucleation theory. For both this experimental technique and a static one developed during the candidate’s Masters degree, mineral dust particulate proved to be the most efficient ice nuclei (IN) activating at RH with respect to ice (RHi) as low as 105% at T = 233 K. The efficiency varied with particle size and aerosol surface area (SA). Large particles or higher SA activated at lower RHi than small particles or lower SA. The static chamber was sensitive to the first ice event out of a large SA and therefore gave true onset RHi, which was lower than the onset defined by the CFDC studies, which was not sensitive to a single ice event. In addition the static chamber used a broader size range of particulate matter, including super micron particles while the CFDC particles sizes were restricted to below 0.5 µm. Soot and organic coated dust particles were inefficient IN compared to pure dust. Soot aerosols showed some efficiency at T < 233K where deposition ice formation was apparent. The hygroscopic organics had intermediate ice activity between dusts and alkyl-organics and soot. Bacteria aerosols were active in the deposition mode for T as high as 247 K. Contact angles () computed for ice germs forming onto natural mineral dust were small, 7<  < 29, at 223 K for RH ranging from ice to water saturation. It was concluded that there is no single value for the onset of ice formation in the atmosphere via deposition freezing. The associated contact angles show that there is a distribution of active sites on IN and that not all active sites have the same affinity for initiation of ice formation even within the same aerosol type. This work provides evidence that deposition mode nucleation can be an alternate pathway to homogeneous nucleation when mineral aerosols are present in the troposphere since the high T - low RH conditions required for deposition mode nucleation are more easily encountered in the atmosphere than the low T - high RH required for homogeneous nucleation.

In this thesis we will investigate the role of diapycnal mixing on the ocean general circulation. This thesis is divided into three main parts. In the first part we show that there exists an almost infinite number of pathways to turbulence in oceanic energetic shear zones at high Reynolds number. Such a large number of accessible routes to truly chaotic motion is not typical of most of the existing body of laboratory and numerical experiments of shear-induced diapycnal mixing, but is shown to be of relevance to diapycnal mixing in geophysical flows. A key finding is that the use of generally accepted empirical relations based on laboratory experiments for the quantification of diapycnal mixing leads to large inaccuracies. In the second part we perform high resolution numerical experiments of diapycnal mixing in the oceanographically relevant high Reynolds number parameter range. Through detailed analysis of the flow energetics and mixing properties of these flows, we show that the net buoyancy flux facilitated by turbulence, the efficiency of diapycnal mixing, and the resultant effective diffusivity, all depend in non-trivial ways on the specific route to turbulence for each individual mixing event. This has important implications for practical methods of estimating an effective diapycnal mixing diffusivity from observations as well as for parametrization of mixing in ocean general circulation models. We show quantitatively that such methods can be inaccurate to the extent that they will need to be completely revised or replaced. In the third and final part of the thesis we investigate the sensitivity of the meridional overturning circulation of the abyssal ocean to the intensity and spatial variations of diapycnal mixing. We show that changes in intensity of mixing by factors well within the errors associated with practical estimates (as discussed above) lead to significant changes in ocean circulation. We show that enhanced abyssal mixing, surface winds, and meso-scale eddies play leading roles in driving the abyssal ocean circulation and in setting the stratification. As an example of the application of our analysis we show that proper parametrization of enhanced abyssal mixing leads to realization of the important role of the (often neglected) geothermal heat flux in driving the Antarctic Bottom Water circulation.

In this thesis we will investigate the role of diapycnal mixing on the ocean general circulation. This thesis is divided into three main parts. In the first part we show that there exists an almost infinite number of pathways to turbulence in oceanic energetic shear zones at high Reynolds number. Such a large number of accessible routes to truly chaotic motion is not typical of most of the existing body of laboratory and numerical experiments of shear-induced diapycnal mixing, but is shown to be of relevance to diapycnal mixing in geophysical flows. A key finding is that the use of generally accepted empirical relations based on laboratory experiments for the quantification of diapycnal mixing leads to large inaccuracies. In the second part we perform high resolution numerical experiments of diapycnal mixing in the oceanographically relevant high Reynolds number parameter range. Through detailed analysis of the flow energetics and mixing properties of these flows, we show that the net buoyancy flux facilitated by turbulence, the efficiency of diapycnal mixing, and the resultant effective diffusivity, all depend in non-trivial ways on the specific route to turbulence for each individual mixing event. This has important implications for practical methods of estimating an effective diapycnal mixing diffusivity from observations as well as for parametrization of mixing in ocean general circulation models. We show quantitatively that such methods can be inaccurate to the extent that they will need to be completely revised or replaced. In the third and final part of the thesis we investigate the sensitivity of the meridional overturning circulation of the abyssal ocean to the intensity and spatial variations of diapycnal mixing. We show that changes in intensity of mixing by factors well within the errors associated with practical estimates (as discussed above) lead to significant changes in ocean circulation. We show that enhanced abyssal mixing, surface winds, and meso-scale eddies play leading roles in driving the abyssal ocean circulation and in setting the stratification. As an example of the application of our analysis we show that proper parametrization of enhanced abyssal mixing leads to realization of the important role of the (often neglected) geothermal heat flux in driving the Antarctic Bottom Water circulation.

Little is currently known regarding the nature and consequences of interactions between photoactive surfaces, including mineral dust and ‘urban film’, and gas-phase pollutants in urban environments. In order to address this knowledge gap, this thesis explores the photochemical reactivity of these environmental surfaces in controlled laboratory settings. The photoenhanced ozonation of pyrene, a toxic product of incomplete combustion, proceeds at different rates and via different mechanisms at three model ‘urban film’ surfaces. These results are important because they suggest that the reactivity of a molecule on simplified surfaces may not accurately reflect its reactivity in the real environment. The photooxidation of isopropanol at the surface of TiO2, here used as a proxy for the photoactive component of mineral dust, yields gas-phase acetone. This chemistry is amplified by nitrate, a major surficial component of atmospherically processed dust. These results suggest that dust has the potential to convert non-absorbing species to photochemically active species, and thereby serve as a source of reactive organic radicals for further gas- or surface-phase chemistry. Oxalic acid, the most atmospherically abundant dicarboxylic acid, is efficiently oxidized to gas-phase CO2 at the surface of Mauritanian sand and Icelandic volcanic ash. These experiments indicate that the lifetime of oxalic acid may be limited in arid regions by Fe and Ti-catalyzed aerosol-phase photochemistry. Fluorotelomer alcohols (FTOHs), a class of industrial chemicals used in the production of surface coatings, undergo photooxidation at the surface of sand and ash to yield toxic and persistent perfluorinated carboxylic acids (PFCAs). These results provide the first evidence that the metal-catalyzed heterogeneous oxidation of FTOHs may act as a local source of aerosol-phase PFCAs. Illumination of Nigerien sand in the presence of gas-phase SO2 leads to the formation of surface-sorbed sulfate. This chemistry proceeds more efficiently on fine sand than on coarse sand. In chamber experiments, the illumination of SO2 in the presence of realistically produced dust aerosol results in new particle formation. Together, these results suggest that SO2 photochemistry at the dust surface has the potential to change not only dust hygroscopicity but also the net scattering potential of dust-containing air masses.

A novel method was developed for producing high-resolution (∼ 11km) maps of surface NO2 concentrations by combining satellite retrieved NO2 columns from OMI with in situ measurements made by permanent monitoring networks. Field data from the BAQS-met field campaign in the Windsor area during 2007 was used to validate this method and explore the uncertainties and biases in the inferred values. Good correlation with the network of passive monitors was found (R = 0.69). Interference of NOz in traditional NO2 measurements was found to be small (0.9 ppb) when considered for 24-hr averages. The inference method was extended to qualitatively analyze long-term trends in Windsor. Comparison against a land-use regression model in Toronto showed similar overall trends, but the downtown core was underestimated considerably by the OMI-inferred map. While the presented inference method can simplify and increase the utility of OMI NO2 data, limitations remain as to the spatial and temporal resolution achievable.

The indirect aerosol effect contributes to major uncertainties in determining the radiation budget of the earth. A large uncertainty is due to the formation of ice clouds onto natural or anthropogenic aerosols. Field studies have shown that mineral type particles are often associated with ice crystals in the mid-upper troposphere and given the long residence time in the atmosphere of dust particles (~2 weeks in the absence of precipitation), their contribution to ice formation processes is not fully defined. In order to probe ice formation onto natural mineral dust in a setting where it could be suspended as aerosol, a new continuous flow diffusion chamber (CFDC) was built. This allowed investigations of the effects of total aerosol surface area and particle size. The CFDC was also used in an international inter-comparison of ice nucleation instrumentation to compare efficiencies of soot, biological aerosol (bacteria) and samples of natural desert dusts from different regions of the world. The laboratory observations were parameterized using nucleation rates (Jhet) and contact angles () as described by classical nucleation theory. For both this experimental technique and a static one developed during the candidate’s Masters degree, mineral dust particulate proved to be the most efficient ice nuclei (IN) activating at RH with respect to ice (RHi) as low as 105% at T = 233 K. The efficiency varied with particle size and aerosol surface area (SA). Large particles or higher SA activated at lower RHi than small particles or lower SA. The static chamber was sensitive to the first ice event out of a large SA and therefore gave true onset RHi, which was lower than the onset defined by the CFDC studies, which was not sensitive to a single ice event. In addition the static chamber used a broader size range of particulate matter, including super micron particles while the CFDC particles sizes were restricted to below 0.5 µm. Soot and organic coated dust particles were inefficient IN compared to pure dust. Soot aerosols showed some efficiency at T < 233K where deposition ice formation was apparent. The hygroscopic organics had intermediate ice activity between dusts and alkyl-organics and soot. Bacteria aerosols were active in the deposition mode for T as high as 247 K. Contact angles () computed for ice germs forming onto natural mineral dust were small, 7<  < 29, at 223 K for RH ranging from ice to water saturation. It was concluded that there is no single value for the onset of ice formation in the atmosphere via deposition freezing. The associated contact angles show that there is a distribution of active sites on IN and that not all active sites have the same affinity for initiation of ice formation even within the same aerosol type. This work provides evidence that deposition mode nucleation can be an alternate pathway to homogeneous nucleation when mineral aerosols are present in the troposphere since the high T - low RH conditions required for deposition mode nucleation are more easily encountered in the atmosphere than the low T - high RH required for homogeneous nucleation.

A novel method was developed for producing high-resolution (∼ 11km) maps of surface NO2 concentrations by combining satellite retrieved NO2 columns from OMI with in situ measurements made by permanent monitoring networks. Field data from the BAQS-met field campaign in the Windsor area during 2007 was used to validate this method and explore the uncertainties and biases in the inferred values. Good correlation with the network of passive monitors was found (R = 0.69). Interference of NOz in traditional NO2 measurements was found to be small (0.9 ppb) when considered for 24-hr averages. The inference method was extended to qualitatively analyze long-term trends in Windsor. Comparison against a land-use regression model in Toronto showed similar overall trends, but the downtown core was underestimated considerably by the OMI-inferred map. While the presented inference method can simplify and increase the utility of OMI NO2 data, limitations remain as to the spatial and temporal resolution achievable.

There is little consensus on what forced the climate of southern Africa to change during the Last Glacial Maximum (LGM). Because of southern Africa's latitudinal position, changes in seasonal precipitation can help resolve the influence of internal climate factors such as groundwater and external climate forcers such as large scale atmospheric circulation patterns. This paper presents a simple model of groundwater discharge based on permeability and topography in comparison with general circulation model precipitation results and paleoenvironmental proxy records. Results show that during the LGM the Intertropical Convergence Zone (ITCZ) likely weakened and moved slightly further south while the westerlies likely expanded slightly northward, with no significant change in strength. The climate and groundwater results were compared to the distribution of LGM and pre-LGM archaeological sites. Results show that the Later Stone Age peoples of southern Africa were likely inhabiting a relatively wet environment rather than an arid one.

There is little consensus on what forced the climate of southern Africa to change during the Last Glacial Maximum (LGM). Because of southern Africa's latitudinal position, changes in seasonal precipitation can help resolve the influence of internal climate factors such as groundwater and external climate forcers such as large scale atmospheric circulation patterns. This paper presents a simple model of groundwater discharge based on permeability and topography in comparison with general circulation model precipitation results and paleoenvironmental proxy records. Results show that during the LGM the Intertropical Convergence Zone (ITCZ) likely weakened and moved slightly further south while the westerlies likely expanded slightly northward, with no significant change in strength. The climate and groundwater results were compared to the distribution of LGM and pre-LGM archaeological sites. Results show that the Later Stone Age peoples of southern Africa were likely inhabiting a relatively wet environment rather than an arid one.

Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.