The Palaeoproterozoic Birimian terrane of the West African Man Shield is a gold province of global importance. Gold mineralization at the Damang deposit, however, is unique amongst known gold deposits in Ghana. It comprises a stratigraphically controlled auriferous quartz-pebble conglomerate, which is overprinted by later orogenic gold contained in a sub-horizontal fault-fracture quartz vein array. Furthermore, this gold mineralization is hosted in sediments of the Tarkwaian System, rather than volcanics of the underlying Birimian Supergroup. This thesis integrates petrological, geochemical, thermodynamic and geochronological data to investigate the Damang deposit in the context of the regional tectonic and metallogenic framework. Staurolite-grade, amphibolite facies peak metamorphism at Damang occurred at around 595ºC and 5.5 kbar at 2005±26 Ma. This was immediately followed by a short period (~ 5 Ma) of rapid exhumation, at a rate of approximately 2.6 mm/yr. This decompression led to the formation of the fault-fracture mesh, which was enhanced by the silicification of host rocks during an earlier ‘Pink Haematite’ hydrothermal event that was associated with the intrusion of voluminous dolerite bodies. Orogenic gold mineralization occurred at the end of this exhumation period at conditions of 400–450ºC and 1–2 kbar. These conditions are in broad agreement with other Ghanaian deposits. A gold-bearing, CO₂-rich (X(CO₂) ~ 0.7), aqueous fluid generated through metamorphic devolatilization reactions close to peak metamorphism and during the subsequent exhumation fed the fault-fracture mesh. This fluid imparted a potassic–carbonation–sulphidation alteration overprint similar to that seen at orogenic gold deposits globally. This alteration signature is characterized and identified with portable infrared spectroscopic techniques. Exhumation rates following gold mineralization were less than 0.01 mm/yr, while ⁴⁰Ar/³⁹Ar dating of biotites give ages ranging between 1978.8±6.2 Ma and 1898±11 Ma, indicating extremely prolonged (~ 80 Ma) cooling through the interval 300–250ºC. Ultimately, this thesis demonstrates that the Damang deposit is part of the same regional metallogenic event that formed the other Ghanaian deposits. This implies that the Tarkwaian System elsewhere in Ghana may be prospective for orogenic gold mineralization.

Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodiumglucose linked transport 2 (SGLT2) inhibitor. Phloridzin never experienced widespread clinical usage in the pharmaceutical market due to its side effects and poor bioavailability when compared to other antidiabetic therapeutics. The poor bioavailability is primarily attributed to the degradation of the glycosidic bond of the phloridzin, resulting in the formation of phloretin, the aglycone of phloridzin and glucose. While phloretin displays a reduced capacity of SGLT2 inhibition, this nutraceutical shows enhanced antineoplastic activity in comparison to phloridzin. Gold nanoparticles (AuNPs) have been explored in improving the bioavailability of many drugs and therefore we opt for gold nanoparticle mediated delivery of phloridzin and phloretin and exploration of their anticancer mechanism. In this study, we have synthesized phloridzin and phloretin conjugated gold nanoparticles (Phl-AuNP and Pht-AuNP) in a single-step, rapid, biofriendly processes. The synthesized AuNPs morphology and elemental composition was characterized via transmission electron microscopy, UV-Vis spectroscopy, scanning electron microscopyenergy dispersive x-ray spectroscopy, and thermogravimetric analysis. Assessment of the antineoplastic potency of the dihydrochalcone-conjugated AuNPs against cancerous cell lines was accomplished through monitoring via flow cytometry. We posit that the functionalization of these chalcones onto the gold nanoparticles’ surface has improved the pharmacokinetic profile of phloridzin and phloretin.

The story of the advancing American frontier has unending interest. Perhaps one of the most colorful and unusual frontier developments was that of the mining frontier in the Rocky Mountains of Colorado. During the years following the discovery of gold in 1858 and the early 1880's occurred an almost unprecedented evolution from a primitive pioneer society to complex industrial development.

Artisanal and small-scale mining (ASM) are important sources of income for impoverished rural populations in many developing countries. Poor labor and environmental conditions often prevail because governments lack the capacity and sometimes the will to responsibly control ASM. At the other end of the supply chain, corporate social responsibility (CSR) strategies increasingly require jeweler’s suppliers to control social and environmental aspects of mining. In a sense, jewelry and mining corporations are voluntarily taking the issue of governance into their own hands. A combination of CSR and revenue-centric development strategies has the potential to further marginalize poor, rural populations who depend on ASM. It is therefore important to examine how ASM has been affected by global social responsibility trends, why it is often left out and to find ways that ASM populations can be successfully integrated into planning for sustainable development and socially responsible business. Gemstones and gold are economically the most important global commodities for ASM populations and precious colored gemstones are rarely mined on a large-scale. Ethnographic research was undertaken to explore how global social responsibility strategies interact with local realities of ASM colored gemstone and gold production. Burma, Madagascar and Colombia each present cases with clear interaction between global CSR trends and ASM, and combined provide a range of public policies with regards to rural populations who depend on ASM. Informal interviews and industry observations were conducted with a range of stakeholders in the global precious mineral trade and mineral development sector. Semi-structured interviews were recorded with key informants for each case study and these were triangulated with internal documents, press releases and articles. Burma illustrates a case where global CSR is attempting to halt ASM because of poor governance and human rights violations. Madagascar illustrates a case where governance and education are improving but widespread poverty and a legacy of corruption has so far prevented the direct integration of ASM into CSR strategies. In the case of Colombia, one region has successfully connected ASM with the global CSR dialogue by designing and implementing a certification program to effectively valorize and govern ASM production. Major findings reveal that (1) CSR in the mineral sector is a contentious and political issue with a range of stakeholder viewpoints; (2) a bottom-up, process-oriented approach can successfully drive economic and social improvement in ASM commodity chains; and (3) community empowerment, education, youth leadership and social networking appear to be key factors for driving production of ASM minerals that can comply with social and environmental standards.

Des nanoparticules d’or fonctionnelles ont été synthétisées avec pour objectifs l’élaboration de nanomatériaux pour applications biomédicales et propriétés physiques originales. L’étude de la fonctionnalisation a conduit à utiliser le chimie “click” entre des nanoparticules d’or portant des ligands thiolates azoturés et des alcynes terminaux en utilisant un catalyseur au cuivre (I) renforcé par un ligand polyazoté, ce qui a permis d’introduire des fonctions très variées. En particulier le récepteur folate a été greffé de cette façon pour la synthèse de nouveaux vecteurs du docétaxel, un puissant agent anti-cancéreux dont l’étude est menée en collaboration. Des nanoparticules d’or fonctionnelles ont aussi servi de support pour le greffage de complexes du fer (II) à transition de spin, ce qui a permis de réaliser l’étude en 2D par différentes techniques physiques en collaboration. Enfin un nouveau ligand azoté a été mis au point pour la synthèse de nanoparticules d’or originales. / The thesis concerns functionalizations and applications of gold nanoparticles (AuNPs). In the aspects of functionalization of AuNPs, we concentrated on efficiently functionalized AuNPs by “Click” chemistry. In the aspects of applications, the PEG capped AuNPs was prepared to encapsulate vitamins, which has a potential use in hydrophobic part of human body; the folate functionalized AuNPs was used for docetaxel delivery for cancer therapy; the novel synthesis of triazole stabilized AuNPs used for biosensors; and the citrate capped AuNPs introduced into the silica thin films to check the SERS effect and spin crossover of iron complexes.

Master of Science / Department of Chemistry / Kenneth J. Klabunde / The motivation for the preparation of gold nanoparticles includes their potential utility in sensors, nanoelectronics, and the vast basic knowledge we can gain from these novel materials. Colloids of gold nanoparticles are also one of the most stable and easiest to manipulate. Synthesizing gold nanoparticles with narrow size distribution, uniform shape, and good crystalline nature represents a significant challenge. Thiols were found to be very efficient capping ligands for the digestive-ripening process in our research group, during which a colloidal suspension in a solvent is refluxed at the solvent boiling temperature in the presence of a capping ligand to convert a highly polydispersed colloid into a nearly monodispersed one. The current thesis research focuses on using amines instead of thiols as the capping ligands, which were also found to have similar efficiency for this purpose. The major part of the work is devoted to understanding the digestive ripening of gold-amine colloids system, and the effect of the nature of the amine ligands. A noteworthy achievement of the current work is the ability to synthesize stable gold colloids with different sizes by using different amine ligands. A diverse set of instrumental techniques is used for the characterization of the gold nanoparticles.

Doctor of Philosophy / Department of Chemical Engineering / Vikas Berry / Nanoscale materials invite immense interest from diverse scientific disciplines as these provide access to precisely understand the physical world at their most fundamental atomic level. In concert with this aim of enhancing our understanding of the fundamental behavior at nanoscale, this dissertation presents research on three nanomaterials: Gold nanoparticles (GNPs), Graphene and ultra-thin Boron Nitride sheets (UTBNSs). The three-fold goals which drive this research are: incorporating mobility in nanoparticle based single-electron junction constructs, developing effective strategies to functionalize graphene with nano-forms of metal, and exfoliating ultrathin sheets of Boron Nitride. Gold nanoparticle based electronic constructs can achieve a new degree of operational freedom if nanoscale mobility is incorporated in their design. We achieved such a nano-electromechanical construct by incorporating elastic polymer molecules between GNPs to form 2-dimensional (2-D) molecular junctions which show a nanoscale reversible motion on applying macro scale forces. This GNP-polymer assembly works like a molecular spring opening avenues to maneuver nano components and store energy at nano-scale. Graphene is the first isolated nanomaterial that displays single-atom thickness. It exhibits quantum confinement that enables it to possess a unique combination of fascinating electronic, optical, and mechanical properties. Modifying the surface of graphene is extremely significant to enable its incorporation into applications of interest. We demonstrated the ability of chemically modified graphene sheets to act as GNP stabilizing templates in solution, and utilized this to process GNP composites of graphene. We discovered that GNPs synthesized by chemical or microwave reduction stabilize on graphene-oxide sheets to form snow-flake morphologies and bare-surfaces respectively. These hybrid nano constructs were extensively studied to understand the effect and nature of GNPs’ interaction with graphene, and applied to address the challenge of dispersing bare-surfaced GNPs for efficient liquid-phase catalysis. We also revisited the functionalization of graphene and present a non-invasive surface introduction of interfaceable moieties. Isostructural to graphene, ultrathin BN sheet is another atomic-thick nanomaterial possessing a highly diverse set of properties inconceivable from graphene. Exfoliating UTBNSs has been challenging due to their exceptional intersheet-bonding and chemical-inertness. To develop applications of BN monolayers and evolve research, a facile lab-scale approach was desired that can produce processable dispersions of BN monolayers. We demonstrated a novel chlorosulfonic acid based treatment that resulted in protonation assisted layer-by-layer exfoliation of BN monolayers with highest reported yields till date. Further, the BN monolayers exhibited extensively protonated N centers, which are utilized for chemically interfacing GNPs, demonstrating their ability to act as excellent nano-templates. The scientific details obtained from the research shown here will significantly support current research activities and greatly impact their future applications. Our research findings have been published in ACS Nano, Small, Journal of Physical Chemistry Letters, MRS Proceedings and have gathered >45 citations.

M.Sc. / Atmospheric emissions of dust and chemicals from gold mine tailings are ongoing environmental management issues on the Witwatersrand, where residential areas have developed in proximity to dumps. Residual amounts of cyanide, used as a chemical in the gold extraction process, are deposited with the mineral tailings. This study deals with the evaluation of population exposure to cyanide vapour emitted from gold mine tailings dams, an issue of environmental impact and public health concern. The first part of this study deals with the determination of the emission factors of cyanide vapour from three selected gold mine tailings dams: one under reclamation; one no longer operational; and one fully operational as a slimes deposition site. These three sites are located in the Boksburg area of the Ekurhuleni Metropolitan Municipality. Twelve samples were collected in all: six from the Cason (2628AAL91) mine dump (under reclamation in 2006); four from the ERPM tailings complex [comprising the dormant deposits 4/L/47, 4/L/48, 4/L/49 and 4/L/50, which are north of the N17 national highway; and the 2628ACL1 deposit, which is south of the N17]; and two from the Rooikraal (active) deposition site. All samples were collected in the year 2006. In the second part of the study, the obtained emission factors were used in an Industrial Source Complex dispersion model to measure the degree of population exposure to cyanide vapour for communities that are in proximity to the operational gold mine tailings dams in the Johannesburg Metropolitan Municipality. In the third part, a health risk assessment was carried out for communities in proximity to the selected gold mine tailings dams. The study revealed the average flux (± std. dev.) of Cason to be (4.7 ± 0.8) x 10-7 g m-2 s-1, the average flux of ERPM (3.9 ± 0.6) x 10-7 g m-2 s-1, the average flux of Rooikraal (1.7 ± 0.2) x 10-5 g m-2 s-1. The concentrations of cyanide vapour emitted from the older tailings deposits (sand) that are under reclamation and the dormant slimes dams are very low (and pose little health risk to occupants of adjacent land). However, HCN emission factors from operational tailings dams, which are receiving continuous depositions, are 3 to 80 times higher than the emission factors from dormant mine tailings. Ambient cyanide concentrations near the active tailings deposits may sometimes exceed selected international health standards. The average hourly, daily and annual dispersion model calculations for the Nasrec tailings deposition sites in Johannesburg revealed that 117 938, 18 722 and 8 130 people respectively were exposed to hydrogen cyanide concentrations that were above international (Ontario, Canada) standards. This raises environmental concerns that require institution of cyanide monitoring and setting of emission limits applicable to South African legal and environmental circumstances. These conclusions are based on a small number of emission factor determinations and hence these findings should be regarded as provisional. Further testing and verification are required for emission factors from a larger number of dormant, reworked and active tailings dams.

M.Tech. (Chemistry) / Please read abstract in the full-text document

M.Sc. / [AuCl(PPh3)] was reacted with mixed thiols in the presence of silver(I) oxide, resulting in complexes of the type [Au(SC6H4X)(PPh3)] X= Cl, NH2,CH2, forming silver chloride as a by-product. In addition to the above series [Au(SCH2(C6H4)3(2-C6H5(C6H4N)] was prepared via a different route, where [AuCl3(2-C6H5(C6H4N)] was reacted with benzyl mercaptan under reflux in the presence of silver(I) oxide for 3 h, forming silver chloride as a by-product. Palladium complex [PdCl2(2-C6H5(C6H4N)] was prepared by reacting [PdCl2(MeCN)] with 2-phenylpyridine at room temperature for 2 h. All complexes were characterized by 1H, 13C, 31P{H} NMR, IR, mass spectrometry and elemental analysis. Characterization of the starting materials [AuCl3(2-C6H5(C6H4N)] and [PdCl2(2- C6H5(6H4N)] by single crystal X-ray diffraction confirmed their chemical formula. All complexes were reacted with sulfur dioxide (SO2) and the reactions were monitored by electrochemistry and UV-vis spectroscopy. The electrochemical study of the complexes, using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), showed one anodic peak, which is due to gold(I/III) and an unresolved peak due to thiolate ligand. Upon bubbling of SO2 to the complexes, there was an immediate change of colour from clear to yellow, the CV results showing an increase in current of the gold(I/III) peak. UV-vis spectroscopy studies showed a shift of peak form 250-286 nm, upon bubbling of SO2 to complexes.