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Air pollutant exposure poses a health risk to humans and impacts negatively on agriculture. High levels of air pollution resulted in extensive crop damage and yield reduction in Europe and USA. The Highveld region in South Africa, a very important area for maize and soya production, has already been declared an air pollution hot spot, with SO2 being the most concerning air pollutant. Most of the SO2 over the Highveld originates from the burning of coal for power generation. Developing countries, such as South Africa, are highly dependent on agriculture for food security and high levels of air pollution pose serious risks to the agricultural industry. Currently very little information is available on the effects of air pollution on crop production in South Africa. This study aimed to establish exposure-response relationship for SO2 on soybean and the quantification thereof on the morphological, physiological and biochemical characteristics. Two soybean cultivars were used, namely: LS 6164 and PAN 1666. The plants were fumigated for 7 hours, 7 days a week with 0 (carbon filtered control; CF), 25, 75 and 150 ppb SO2. The effect of SO2 was investigated on the growth, photosynthetic capabilities, photosynthetic gas exchange, peroxidase activity and lipoxygenase activity of the cultivars. Foliar injuries and interveinal chlorosis were visible with increasing levels of SO2 as well as a decrease in biomass accumulation, especially in root biomass; a more prominent feature of LS 6164. The number of nodules of both cultivars decreased insignificantly as the levels of SO2 increased. The number of pods per plant and the average weight of 30 seeds indicated a downward trend with an increase in SO2 concentration. The chlorophyll content of PAN 1666 was lower compared to LS 6164. PAN 1666 had the largest reduction in stomatal conductance at 150 ppb SO2 fumigation. The photosynthetic vitality index indicated that LS 6164 was more sensitive to SO2 inhibition from 25 ppb SO2 and higher, whereas PAN 1666 mostly became sensitive to SO2 from 75 ppb SO2. A decrease in the ability to absorb light energy, the trapping of excitation energy to transfer electrons beyond QA-, and the reduction of end electron acceptors all contributed to the decline in the vitality index. Sulphur content increased significantly in the 75 ppb and 150 ppb treatments of both cultivars. Induced peroxidase and lipoxygenase activity was seen in both cultivars, especially at higher concentrations of SO2 treatments. PAN 1666 had a higher rate of peroxidase and lipoxygenase activity compared to LS 6164. The implication for SO2 on crop production in the highly industrial Highveld area was demonstrated to be potentially of great concern. The dose-response relationships plotted for OJIP parameters emphasized that SO2 is an inhibitor of photosynthesis and phytotoxic of nature. Both cultivars experienced limitations from 75 ppb, especially at the 150 ppb SO2 concentration. From these results it appears that PAN 1666 is more adapted to SO2 compared to LS 6164 and levels of 75 ppb SO2 and higher become toxic to these plants. / Thesis (Master of Environmental Sciences)--North-West University, Potchefstroom Campus, 2013

Air pollutant exposure poses a health risk to humans and impacts negatively on agriculture. High levels of air pollution resulted in extensive crop damage and yield reduction in Europe and USA. The Highveld region in South Africa, a very important area for maize and soya production, has already been declared an air pollution hot spot, with SO2 being the most concerning air pollutant. Most of the SO2 over the Highveld originates from the burning of coal for power generation. Developing countries, such as South Africa, are highly dependent on agriculture for food security and high levels of air pollution pose serious risks to the agricultural industry. Currently very little information is available on the effects of air pollution on crop production in South Africa. This study aimed to establish exposure-response relationship for SO2 on soybean and the quantification thereof on the morphological, physiological and biochemical characteristics. Two soybean cultivars were used, namely: LS 6164 and PAN 1666. The plants were fumigated for 7 hours, 7 days a week with 0 (carbon filtered control; CF), 25, 75 and 150 ppb SO2. The effect of SO2 was investigated on the growth, photosynthetic capabilities, photosynthetic gas exchange, peroxidase activity and lipoxygenase activity of the cultivars. Foliar injuries and interveinal chlorosis were visible with increasing levels of SO2 as well as a decrease in biomass accumulation, especially in root biomass; a more prominent feature of LS 6164. The number of nodules of both cultivars decreased insignificantly as the levels of SO2 increased. The number of pods per plant and the average weight of 30 seeds indicated a downward trend with an increase in SO2 concentration. The chlorophyll content of PAN 1666 was lower compared to LS 6164. PAN 1666 had the largest reduction in stomatal conductance at 150 ppb SO2 fumigation. The photosynthetic vitality index indicated that LS 6164 was more sensitive to SO2 inhibition from 25 ppb SO2 and higher, whereas PAN 1666 mostly became sensitive to SO2 from 75 ppb SO2. A decrease in the ability to absorb light energy, the trapping of excitation energy to transfer electrons beyond QA-, and the reduction of end electron acceptors all contributed to the decline in the vitality index. Sulphur content increased significantly in the 75 ppb and 150 ppb treatments of both cultivars. Induced peroxidase and lipoxygenase activity was seen in both cultivars, especially at higher concentrations of SO2 treatments. PAN 1666 had a higher rate of peroxidase and lipoxygenase activity compared to LS 6164. The implication for SO2 on crop production in the highly industrial Highveld area was demonstrated to be potentially of great concern. The dose-response relationships plotted for OJIP parameters emphasized that SO2 is an inhibitor of photosynthesis and phytotoxic of nature. Both cultivars experienced limitations from 75 ppb, especially at the 150 ppb SO2 concentration. From these results it appears that PAN 1666 is more adapted to SO2 compared to LS 6164 and levels of 75 ppb SO2 and higher become toxic to these plants. / Thesis (Master of Environmental Sciences)--North-West University, Potchefstroom Campus, 2013

Australia has the largest economical lignite resources in the world. However, the utilisation of lignite is faced with a number of technical, economical and environmental problems due to its high moisture content and some of the deposits containing high sulphur and high inorganic matter. During pyrolysis, the first step of any thermochemical conversion processes of coal, some of the sulphur in lignite evolves as sulphur-bearing volatiles while others are retained in the solid phase of the lignite char. The present research aims to study the sulphur transformation during pyrolysis of Australian lignite. The specific objectives of this research include a study on the transformation of pyrite, sulphate and organic sulphur during lignite pyrolysis as well as an investigation of the effect of inorganic matter on the sulphur transformation during lignite pyrolysis. To help the interpretation of sulphur transformation, the lignite samples were characterised using a combination of analytical techniques, i.e. X-ray diffraction (XRD), X-ray fluorescent (XRF), ion chromatography (IC), Scanning electron microscope equipped with an energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infra red (FTIR), solid state 13C nuclear magnetic resonance (NMR) and petrographic analysis. Pyrolysis was carried out in a thermogravimetric analyser (TGA) and fixed bed reactor. The lignites and their chars were analysed for sulphur forms using a carbon sulphur (CS) analyser. To study the volatiles released during pyrolysis, experiments were also performed using a TGA coupled to a mass spectrometer (TGA-MS). Eleven (11) Australian lignite samples, denoted as L1 to L11, respectively, from the same lignite deposit but with different sulphur and inorganic matter concentrations were employed in this study. They are categorised as of low quality since they contain high Executive Summary Sulphur Transformation during Pyrolysis of an Australian Lignite v moisture, very high ash, low fixed carbon and thus they have low calorific value, except for L1. The lignites contain considerable amount of total sulphur, except for L1. Mineralogy of the lignites showed that the lignites contain extremely high sodium and chlorine. FTIR and solid state 13C NMR spectroscopy confirmed that oxygenated functional structures are significantly present in the lignites.

The utilisation of waste process grease (WPG) as feedstock for biodiesel production was investigated in this study. WPG is a lubrication oil used in the metalworking industry and is considered a hazardous waste material. WPG contains vegetable oil and animal fat which are used as base oils in the lubricant formulation. Three different production routes were followed to produce biodiesel using WPG as feedstock. The first production route involved the conventional two-step production process comprising the acid esterification of the free fatty acids, followed by alkaline transesterification. The second production route involved the extraction of free fatty acids in the WPG by means of liquid-liquid extraction and the production of biodiesel from the extracted free fatty acids through acid esterification. The produced biodiesel was purified by means of chromatography. A third process route was the saponification of the WPG using aqueous sodium hydroxide followed by acidulation with hydrochloric acid. The resulting acid oil was purified by means of column chromatography, using a hydrophobic resin as the stationary phase prior to esterification through acid catalysis to produce biodiesel. The crude biodiesel was purified using column chromatography with silica gel as stationary phase. The optimum reaction conditions for the reduction of the free fatty acid content of WPG in route 1 to 0.5% were a methanol to oil ratio of 8:1 and a reaction temperature of 65 °C with a catalyst loading of 4 wt%. Acetonitrile was found to be the most effective extraction solvent for the reduction of sulphur compounds in the free fatty acid feedstock in route 2. A reverse phase chromatographic system with a hydrophobic stationary phase and methanol as the mobile phase was found to be an effective system to reduce the sulphur to below 10 ppm as specified by the SANS 1935 biodiesel standard in route 3. Both the conventional two-step process (route 1) and the liquid-liquid extraction process (route 2) were found not to be suitable for the production of biodiesel from WPG as the sulphur content of the produced biodiesel for routes 1 and 2 was 8 141 ppm and 4 888 ppm, respectively. The sulphur content of the produced biodiesel following route 3 was 9 ppm. The latter approach reduced the sulphur content of the biodiesel to acceptable levels that conform to the SANS 1935 standard to be used in a B10 biodiesel blend. A biodiesel yield of 45%, calculated as the mass of biodiesel produced as a percentage of the total mass of dried WPG used, was achieved with route 3. The biodiesel conformed to most of the specifications in the SANS1935 standard for biodiesel. The presence of a relatively high concentration of saturated fatty acids reflected in the higher cetane number of 74.7, the high cold filter plugging point of +10 and the oxidative stability of > 6 hours. A comparative cost analysis for route 3 indicated that the production cost of biodiesel, compared to the cost of petroleum diesel is marginally higher at the current Brent crude oil price of $102.41 per barrel. The production of biodiesel from WPG will be economically viable once the crude oil price has risen to about $113 per barrel. / Thesis (PhD (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013.

The utilisation of waste process grease (WPG) as feedstock for biodiesel production was investigated in this study. WPG is a lubrication oil used in the metalworking industry and is considered a hazardous waste material. WPG contains vegetable oil and animal fat which are used as base oils in the lubricant formulation. Three different production routes were followed to produce biodiesel using WPG as feedstock. The first production route involved the conventional two-step production process comprising the acid esterification of the free fatty acids, followed by alkaline transesterification. The second production route involved the extraction of free fatty acids in the WPG by means of liquid-liquid extraction and the production of biodiesel from the extracted free fatty acids through acid esterification. The produced biodiesel was purified by means of chromatography. A third process route was the saponification of the WPG using aqueous sodium hydroxide followed by acidulation with hydrochloric acid. The resulting acid oil was purified by means of column chromatography, using a hydrophobic resin as the stationary phase prior to esterification through acid catalysis to produce biodiesel. The crude biodiesel was purified using column chromatography with silica gel as stationary phase. The optimum reaction conditions for the reduction of the free fatty acid content of WPG in route 1 to 0.5% were a methanol to oil ratio of 8:1 and a reaction temperature of 65 °C with a catalyst loading of 4 wt%. Acetonitrile was found to be the most effective extraction solvent for the reduction of sulphur compounds in the free fatty acid feedstock in route 2. A reverse phase chromatographic system with a hydrophobic stationary phase and methanol as the mobile phase was found to be an effective system to reduce the sulphur to below 10 ppm as specified by the SANS 1935 biodiesel standard in route 3. Both the conventional two-step process (route 1) and the liquid-liquid extraction process (route 2) were found not to be suitable for the production of biodiesel from WPG as the sulphur content of the produced biodiesel for routes 1 and 2 was 8 141 ppm and 4 888 ppm, respectively. The sulphur content of the produced biodiesel following route 3 was 9 ppm. The latter approach reduced the sulphur content of the biodiesel to acceptable levels that conform to the SANS 1935 standard to be used in a B10 biodiesel blend. A biodiesel yield of 45%, calculated as the mass of biodiesel produced as a percentage of the total mass of dried WPG used, was achieved with route 3. The biodiesel conformed to most of the specifications in the SANS1935 standard for biodiesel. The presence of a relatively high concentration of saturated fatty acids reflected in the higher cetane number of 74.7, the high cold filter plugging point of +10 and the oxidative stability of > 6 hours. A comparative cost analysis for route 3 indicated that the production cost of biodiesel, compared to the cost of petroleum diesel is marginally higher at the current Brent crude oil price of $102.41 per barrel. The production of biodiesel from WPG will be economically viable once the crude oil price has risen to about $113 per barrel. / Thesis (PhD (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013.

Sulphur is an important nutrient to plants, and reports of its deficiency have been increasing worldwide. Sulphur starvation causes losses in both yield and quality, and it reduces nitrogen use efficiency of plants. As the timing for fertilisation can be decisive for avoiding deleterious effects, improvements in the description of the sulphur balance in fields are a valuable contribution for assisting fertiliser management. Sulphate is the most important inorganic form of sulphur in soils. Being the mobile form, sulphate is readily available for plants, and also prone to be leached. Therefore the description of the movement of sulphate is the key component of the sulphur balance. Leaching of sulphate from the soil can be significantly delayed by its adsorption onto the soil particles. Soil type and pH are the main factors defining the sulphate adsorption capacity; although the presence of other ions in the soil solution can have a considerable effect. It has been reported that in some soils, typically volcanic and tropical soils with variable-charge characteristics, the co-presence of sulphate and calcium can substantially enhance their retention via ion-pair adsorption (IPA). To determine the influence of cations on the movement of sulphate, series of batch and miscible displacement experiments were conducted using two New Zealand soils, of contrasting ion adsorption capacities: the Taupo sandy and Egmont loam soils. These experiments demonstrated the occurrence of cooperative adsorption of sulphate and calcium in the Egmont soil, but not in the Taupo soil. Batch experiments were conducted to examine the IPA adsorption process in the Egmont soil in more detail. Based on the analyses of the results from these two series of experiments, plus the review of published data, three different mathematical approaches for evaluating the amount of solute adsorbed as ion-pairs are proposed. A computer program was built for solving an adsorption model using these three approaches, and was used to compare the model's predictions and the observed adsorption data. An extension of this program, coupling the adsorption model with a solute transport description, was used to simulate the movement of sulphate and calcium. Comparisons between the data from the miscible displacements and the results from this model are used to demonstrate the applicability of the proposed IPA description for modelling the transport of these ions in the soil. Finally, results from a pot trial with Egmont soil are used to examine the relevance of IPA for the movement of sulphate under non-equilibrium conditions, and with active plant growth. Although the results from this experiment regarding IPA were statistically non-significant, some insights could be obtained and are discussed. More studies involving IPA under non-equilibrium experiments are needed for a better understanding of the relevance of IPA in field conditions.

Dans le cadre des études portant sur l’impact de l’aviation sur le changement climatique, les traînées de condensation font partie des phénomènes présentant le plus d’incertitudes quant à leur rôle. Dans ce contexte, l’étude vise à mieux décrire les caractéristiques physico-chimiques du panache dans le champ proche d’un avion, celles-ci pouvant conditionner les propriétés des traînées de condensation formées.Pour cela, des simulations spatiales tridimensionnelles de type RANS ont été réalisées à l’aide du code CEDRE de l’ONERA, prenant en compte les processus microphysiques, les réactions chimiques, et l’écoulement aérodynamique autour et dans le sillage d'une configuration réaliste d'un avion de transport civil. Les modèles microphysiques intégrés permettent de décrire les processus d’activation des particules de suie et les processus de condensation et d’évaporation d’eau à leur surface.Une phase de validation du code a été menée pour chacun des processus pris en compte, montrant un bon accord avec les données de la littérature. Des études de sensibilité ont également été conduites afin d’évaluer l’impact des paramètres atmosphériques et des caractéristiques des effluents sur les propriétés des cristaux de glace formés. L’augmentation de la teneur en soufre du carburant entraîne un accroissement de l’activité des suies et aboutit à une distance d’apparition plus courte et une opacité plus élevée des traînées de condensation. Lorsque la quantité d’eau émise est suffisante, l’augmentation du nombre de suies éjectées entraîne un accroissement de la concentration de glace, résultant en un fort accroissement de l’opacité et de la superficie de la traînée de condensation. / In the framework of the impact of aviation on climate change studies, the involvement of contrails is identified as one of the most uncertain components. In this context, this study aims to better describe the physico-chemical properties of the plume in the near-field of an aircraft, for they could be critical to contrails properties.To this end, RANS spatial simulations have been performed using the code CEDRE of ONERA, taking into account the microphysical processes, chemical reactions, and the air flow around and in the wake of a realistic civil transport aircraft. Microphysical models have been implemented in order to describe the soot activation processes and the condensation and evaporation of water upon their surface.A validation phase of the code has been carried out for each of the processes taken into account, showing good agreements with data from the literature. Sensitivity studies have also been performed in order to assess the impact of atmospheric parameters and exhaust characteristics on formed contrails properties. The increase of the fuel sulphur content leads to increased soot activation that results in a shorter contrail onset and increased contrail opacity. If the amount of emitted water is sufficient, the increase of the number of ejected soot particles causes an increase of ice concentration that results in an important increase of contrail opacity and surface area.