Philosophiae Doctor - PhD / Coal fly ash has been studied extensively to understand the environmental impacts associated with its disposal, management and reuse. Although several beneficiation processes have been proposed, there has been little or no emphasis on the environmental safety of such processes, products and wastes. Elemental analysis has revealed that toxic elements and radionuclides are present in coal fly ash. Rare earth elements (REE) such as La, Ce and Y are also present in significant amounts in coal fly ash. The aims of this study were to determine the total elemental composition of coal fly ash using different analytical techniques; to validate the application potentials of fly ash beneficiation processes in terms of their environmental safety; and to valorise coal fly ash with a view of recovering REE either by concentrating or leaching the REE in the coal fly ash, products or waste from the beneficiation processes. The beneficiation processes studied were treatment of acid mine drainage (AMD) with fly ash; and the synthesis of geopolymer from fly ash. The fresh fly ash sample used in this study was collected directly from the hoppers at Matla power station and the AMD sample was collected from Carletonville goldmine. A total of 54 major, trace and REE were accurately determined in the ash using different analytical techniques. It was shown that the elemental content of Matla fly ash was of the same order as the SRM NIST coal fly ash 1633b. The comparative study of the four analytical techniques established that ENAA can accurately determine the major, minor and trace elements; that XRF is best suited for the determination of the major and minor elements, whilst the LA ICP-MS is reliable for trace elements determination. The solid residue (AMD/FA) resulting from the AMD interaction with fly ash was characterized with fly ash and the results compared. The results revealed that the amounts of La (141.09 ± 3.85 mg/kg), Ce (27.45 ± 2.04 mg/kg), and Nd (63.73 ± 0.05 mg/kg) in AMD/FA residue was considerably higher than their average abundance in the earth crust that varies from 66 mg/kg in Ce and 40 mg/kg in Nd to 35 mg/kg in La. The results also showed that the AMD/FA residue contained As (11.39 ± 1.21 mg/kg), Cd (3.77 ± 0.02 mg/kg), Cr (72.43 ± 1.27 mg/kg), Hg (10.50 ± 0.85 mg/kg), Ni (124.15 ± 1.6 mg/kg) and Pb (22.46 ± 1.43 mg/kg) which are potentially harmful if leached in to the environment in excessive amounts.

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This thesis was submitted to the Faculty of Arts and Sciences in partial fulfillment of the requirements for the degree Bachelor of Science. / Field observation at seven outcrops and subsequent polished section studies reveal that lead and zinc mineralization in the Hamilton vicinity occurred after the lithification of the host carbonates. The availability of open structures and the presence of potential reducing agents are the main controlling factors of sulphide deposition, The absence of an igneous source demands an origin of the metals from the sedimentary country rocks. Analysis of 14 shales and 12 dolomites by atomic absorption for Cu, Pb, and Zn indicates that the argillaceous rocks are potential source of the heavy metals. Furthermore, a simple leaching experiment has demonstrated that concentrated brine (sodium chloride solution) can preferentially leach lead and zinc from the shales. A mode of origin involving preferential_leaching can then adequately explain the scarcity of copper minerals in the Mississippi Valley-Type ore. It is suggested that better controlled leaching experiments at various temperatures should be done in conjunction with more extensive field work to check the plausibility of such a theory. / Thesis / Bachelor of Science (BSc)

Due to the increasing use of electronic components and the accelerated rate in which these components become obsolete, there has been a dramatic increase of discarded electronic waste (E-waste). E-waste includes obsolete electronic products such as computers, scanners, cellular phones, etc. These electronic components are manufactured using a variety of hazardous materials. As these components are discarded, the toxic and hazardous substances may become mobile and could impact human health and the environment. The toxic substances of concern contained in E-waste include heavy metals and brominated flame retardants (BFRs). This study attempts to identify the leaching potential of BFRs and metals.

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Historically, environmental research associated with Appalachian coal surface mines focused on acid mine drainage and reclamation. Recent studies suggest that electrical conductivity (EC) levels above 500 ?S cm-1 can impair Appalachian streams, shifting the focus towards limiting release of total dissolved solids (TDS) and associated elements of concern. Previous column studies utilized an unsaturated bi-weekly leaching design to evaluate the behavior of overburden with respect to TDS, pH, and trace metals. The objective of this study was to determine the effects of column saturation, leaching solution chemistry, and leaching cycle on the release of TDS and associated elements from an unweathered sandstone. Treatments evaluating potential saturation, leaching solution pH, and leaching cycle included saturated, standard method, vacuum, and standpipe fitted columns; simulated acid rain, de-ionized water, and CaCO3 leaching solutions; and 2x week-1, 1x week-1, 2x month-1, and 1x day-1 leaching cycles. Saturation level in the column significantly impacted leachate pH, EC level, and the release of sulfate, bicarbonate, and associated cations by potentially affecting trace sulfide oxidation and carbonate dissolution reactions. Little evidence of saturation was noted with the standard method. Leaching solution bulk chemistry did not alter leachate chemistry. Longer times between dosing cycles corresponded to higher EC, bicarbonate, and associated cation levels, especially over time. Sulfate, Ca, and Se exhibited the greatest percent release based on total mass losses during peak elution. For managing TDS, time between precipitation events and saturation level can strongly affect short and long-term EC level, its major contributors, and elements of concern. / Master of Science

With a growing population but scarce primary phosphorus sources, recycling of the vital element has become an important research area throughout the last decades. Several streams in society are potential resources for recirculation but municipal sewage is considered one of the most available materials. With current technologies in wastewater treatment, over 95 % of the influent phosphorus is captured in the sludge along with a variety of other nutrients. However, due to increasing fractions of pharmaceutical residues and heavy metals also following the sludge, direct use as fertiliser is being phased out in most European countries in favour of extraction methods. Extraction of nutrients from the sludge is problematic mainly because of dewaterability difficulties. Thus, pretreatment of the material is required to access the desired components at a reasonable cost and energy consumption. Hydrothermal carbonisation (HTC) is a technology showing high potential for treatment of wet carbonaceous material without necessity of prior drying. The resulting product is hygenised, essentially free from pharmaceuticals and easily dewatered. In this Master’s thesis principal conditions for release of phosphorus from HTC converted digested sludge under acid leaching have been experimentally investigated. Dependence of time, temperature, dry solids (DS) content of HTC sludge and pH have been studied. Also, differences arising from acid type have been considered by comparing acidulation with sulphuric acid and hydrochloric acid. A short investigation of the recovery of the dissolved phosphorus from leachate by precipitation was also performed where calcium ions were added to both sulphuric and hydrochloric acid leachates. Extraction of phosphorus from HTC converted sludge has shown to be easier than from pure metal phosphates under comparable leaching conditions and pH values. Also, the dissolved phosphorus concentrations obtained in the presence of HTC converted sludge was higher than for theoretical equilibrium concentrations where all phosphorus is in the form of iron(III) or aluminium(III) phosphate. A maximum leachate phosphorus concentration was around 2500 mg/L, recorded in leaching experiments performed at a dry HTC product concentration of 10 % (w/w) in an extraction solution of water acidified with sulphuric acid. Leaching procedures performed at pH values between 2 and 1 with 1 and 5 % DS HTC product resulted in dissolution of 90 % of ingoing phosphorus at an acid charge of 0.5 kg H2SO4/kg DS HTC product. At this chemical charge, release of phosphorus from converted sludge is fast. Similar amounts of dissolved phosphorus were recorded after 15 min as after 16 h retention time. Possibly, time dependence becomes relevant at lower charges. The dissolution of phosphorus is negatively affected by temperature increases at moderate acid loads, and by possibly by hydrochloric acid at pH values below 2. Addition of calcium gave a dissolved phosphorus reduction of 99.9 % in both the sulphuric acid and hydrochloric acid leachates. Gypsum, CaSO4, also precipitates from the sulphuric acid leachate resulting in 67 % more dry mass. Due to high release of metals during acidulation, the precipitate was also contaminated with large fractions of metals in addition to calcium. In summary, this investigation has demonstrated that up to 90 % of the phosphorus content of the HTC converted sludge can be released by acid leaching, and almost 100 % of the phosphorus can be recovered from the leachate by precipitation with calcium ions.