Em reatores biológicos anaeróbios adequadamente projetados, 'SO IND.4'POT.2-' pode ser reduzido a sulfeto pelas bactérias redutoras de sulfato (BRS), o qual, posteriormente, pode ser oxidado a enxofre elementar, em presença de baixas concentrações de oxigênio dissolvido ('< OU =' 0,1 mg/L). Na presente tese, o processo de biodessulfatação foi estudado em reatores anaeróbios operados em bateladas seqüenciais, com biomassa imobilizada em espuma de poliuretano (PU) e em carvão vegetal (CV), previamente selecionados por testes de adesão microbiana em reatores diferenciais. Posteriormente, avaliou-se o efeito de etanol sobre o desempenho do processo de biodessulfatação. As principais rotas de utilização de substratos orgânicos pelos microrganismos foram identificadas por meio de modelação cinética. A comunidade microbiana foi avaliada por hibridação in situ com fluorescência (FISH). Após o processo de biodessulfatação, avaliou-se o processo de oxidação parcial do sulfeto, em reator aeróbio operado em bateladas seqüenciais, com biomassa imobilizada em PU. Concluiu-se por FISH que as características intrínsecas dos materiais suportes influenciam o equilíbrio microbiano. A relação DQO/['SO IND.4'POT.2-'] igual a 1,3 representou a melhor condição para o processo de biodessulfatação, com PU e com CV como materiais suporte, com eficiência média em redução de sulfato igual a 96%. A adição de etanol melhorou o processo de redução de sulfato. Sulfeto gerado no processo de biodessulfatação foi oxidado parcialmente a enxofre elementar, com eficiência de remoção de 80% no reator aeróbio / In anaerobic biological systems for wastewater treatment well-designed sulphate can be reduced to sulfide by sulphate-reducing bacteria (SRB), and it can be subsequently oxidized to elemental sulphur, under low dissolved oxygen concentration ('< OU =' 0.1 mg/L). The present thesis evaluates the microbial sulphate reduction process in anaerobic sequencing batch biofilm reactors with immobilized biomass in polyurethane foam (PU) and vegetable coal (CV). Such support materials were previously selected by microbial adhesion tests executed in differential reactors. Afterwards, the effect of ethanol addition on the performance of sulphate reduction process was assessed. The main metabolic pathways of organic substrate utilization by microorganisms were identified by kinectic modelation. The microbial community was evaluated by fluorescence in situ hybridization (FISH). The partial sulfide oxidation process was also evaluated in aerobic sequencing batch reactor containing biomass immobilized in PU matrices. It was concluded by FISH that characteristics of the support materials has influence on the microbial equilibrium. The COD/['SO IND.4'POT.2-'] ratio equal to 1.3 provided the best condition for microbial sulphate reduction process in both reactors with mean efficience of 96%. The ethanol addition improved the sulphate reducing process. The sulfide generated was partialy oxidized to elemental sulphur in the aerobic reactor with removal efficience of 80%

The ‘giant’ Tambogrande volcanogenic massive sulphide (VMS) deposits within the Cretaceous Lancones basin of northwestern Perú are some of the largest Cu-Zn-Au-Ag-bearing massive sulphide deposits known. Limited research has been done on these deposits, hence the ore forming setting in which they developed and the key criteria that permitted such anomalous accumulation of base-metal sulphides are not understood. Based on field relationships in the host volcanic rocks and U-Pb geochronology, the deposits formed during the early stages of arc development in the latest Early Cretaceous and were related to an extensional and arc-rift phase (~105-100 Ma, phase 1). During this time, bimodal, primitive basalt-dominant volcanic rocks were erupted in a relatively deep marginal basin. Phase 1 rhyolite is tholeiitic, M-type, and considered to have formed from relatively high temperature, small batch magmas. The high heat flow and extensional setting extant during the initial stages of arc development were essential components for forming a VMS hydrothermal system. The subsequent phase 2 (~99-91 Ma) volcanic sequence comprises more evolved mafic rocks and similar, but more depleted, felsic rocks erupted in a relatively shallow marine setting. Phase 2 is interpreted to represent late-stage arc volcanism during a waning extensional regime and marked the transition to contractional tectonism. The Tambogrande deposits are particularly unusual amongst the ‘giant’ class of VMS deposits in that deposition largely occurred as seafloor mound-type and not by replacement of existing strata. Paleomorphology of the local depositional setting was defined by seafloor depressions controlled by syn-volcanic faults and rhyolitic volcanism. The depressions were the main controls on distribution and geometry of the deposits and, due to inherently confined hydrothermal venting, enhanced the efficiency of sulphide deposition. Geochemical and radiogenic isotope data indicate that the rhyolites in the VMS deposits were high temperature partial melts of the juvenile arc crust that had inherited the isotopic signatures of continental crust. Moreover, Pb isotope data suggest the metal budget was sourced almost wholly from mafic volcanic strata. Therefore, unlike the implications of many conventional models, the felsic volcanic rocks at Tambogrande are interpreted to have only played a passive role in VMS formation. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

The Mount Ayliff Complex (MAC) is situated on the border between Kwa-Zulu Natal and the Eastern Cape provinces in the Republic of South Africa, approximately 90 km due west of Port Shepstone. The Complex forms part of the Karoo Igneous Province and includes five lobes (Ingeli, Insizwa, Tonti, Tabankulu, and Horseshoe) that are the remnants of a single continuous intrusive sheet that had an original extent of 18,000km2• The current outcrop is estimated at 800km2• The lobes all show extensive internal differentiation, from basal ultramafic cumulates to diorites and monzonites at the top, while most other intrusions in the Karoo Igneous Province cooled rapidly enough to produce relatively homogenous dolerites. Most work conducted on the Complex thus far has centered on the Insizwa lobe due to the presence of a Ni-sulphide occurrence near the base of the lobe at Waterfall Gorge. The setting of the ores has analogies to the Noril'sk-Talnakh deposits, which has raised considerable exploration interest on the Mount Ayliff Complex over the last century. The current study investigates the Ni-Cu sulphide potential of the Ingeli and Horseshoe lobes, which have been poorly studied in the past. To this effect, a stream sediment survey was conducted around the Ingeli lobe to try and detect potentially hidden magmatic sulphide ores. Further, the five lobes of the Complex have been compared in terms of lithology and lithogeochemistry. Analytical techniques used for the current study include: XRF, ICP-MS and electron microprobe. Stream sediment samples were analysed using XRF and ICP-OES. Olivines from the ultramafic cumulates of the Ingeli and Insizwa lobes are undepleted in Ni, whereas olivines from the Horseshoe and Tabankulu lobes are strongly depleted in Ni. This suggests that the rocks of the latter two lobes crystallized from parental magmas that interacted with a sulphide liquid and that the magmatic flow direction was from the north to the south. The data indicate that the ultramafic rocks of the Complex plot on or near control lines between olivine and Karoo dolerite indicating that the rocks are mixtures of cumulus olivine and trapped melt of Karoo dolerite composition. There appears to be a copper enrichment towards the top of the ultramafic package in the Ingeli lobe. This pattern corresponds to other studies conducted in the InsiZWa lobe and suggests that the two lobes had originally been connected. The lowermost cumulates of the Ingeli lobe contain an enhanced crustal component suggesting some in situ contamination. No significant sulphide enrichments were encountered in the Basal Zone rocks of the Ingeli lobe. However, the stream sediment data indicate localized PGE enrichment indicating the possible presence of a localized hidden sulphide occurrence of the type found at Waterfall Gorge. Small amounts of sulphides were found associated with the Basal Zone rocks in the Horseshoe lobe consistent with the trends of Ni-depletion of olivines. However, a lack of Co depletion in the ultramafic rocks of this lobe suggests that any sulphide segregation event that did take place was of a relatively small scale. / Dissertation (MSc)--University of Pretoria, 2006. / Geology / MSc / Unrestricted

No description available.

Department of Mining and Environmental Geology / MESMEG

Heavy metal contamination in the environment is a global issue that is likely to increase in the future. This report investigates a construction area in which increased concentrations of the heavy metals cadmium, cobalt, copper, nickel and zinc and a decreased pH-value has been observed in the surface water recipient. The focus is on assessing contamination characteristics and identifying suitable remediation methods to avoid a river protected by environmental quality standards further downstream from getting contaminated. The bedrock in the area is sulphide containing and releases acidic leachate when oxidising, which is assumed to have occurred due to plane blasting and filling of residual rock. The contamination characteristics were assessed with the statistical methods modified double mass analysis and principal components analysis. A water balance was established to obtain the flowrates, discharge volumes and to determine the masses of the released metals in the surface water. Identification of suitable remediation methods was performed through a literature study of available remediation methods and using the findings of the assessments as basis. The results showed that there was a significant increase in metal concentrations and decrease in pH-value roughly around the same time as blasting and filling of residual rocks in the area was begun and that there were elevated levels of sulphide and sulphur, but they could not be specifically linked to any media. The yearly masses of metals released from the area into the surface water were between 77-98 % higher than allowed by the established guidelines. By separating the water assumed to carry the majority of the contaminants from the remaining natural water in the watershed, the volume that needs to be treated can be halved. As the contamination is so extensive, a mixture of remediation methods was proposed, including installing green roofs to decrease the runoff from the area, confining the crushed rock with bentonite and installing a filter for fast, efficient reduction. For long-term remediation, it is suggested to optimise the existing sedimentation basins and wetlands. The conclusions were that it will be very expensive to remediate the contamination, due to the extent and magnitude, and that handling sulphide containing bedrock for construction purposes should be legally regulated in order to avoid negative environmental and economic impacts. / Förorening av tungmetaller i naturen är ett globalt problem som troligtvis kommer öka i framtiden. Den här rapporten undersöker en byggarbetsplats där ökade koncentrationer av metallerna kadmium, kobolt, koppar, nickel och zink samt ett minskat pH-värde har observerats i ytvattenrecipienten. Fokus ligger på att analysera föroreningskaraktärer och identifiera lämpliga åtgärdsmetoder för att undvika att en å nedströms som är skyddad av miljökvalitetsnormer ska förorenas. Berggrunden i området är sulfidförande och släpper ut surt lakvatten när den oxiderar, vilket är antaget har hänt till följd av plansprängning och utfyllnad av överblivet bergmaterial. Föroreningskaraktärerna analyserades med de statistiska metoderna modified double mass analysis och principalkomponentsanalys. En vattenbalans etablerades för att ta fram flöden, volymer och för att bestämma massorna av de frigjorda metallerna i ytvattnet. Identifiering av lämpliga åtgärdsmetoder gjordes med en litteraturstudie av tillgängliga metoder som grund. Resultaten visade att det är en signifikant ökning av metallkoncentrationer och minskning i pH-värde runt samma tid som sprängning och utfyllning av bergmaterial påbörjades samt att det är förhöjda halter av sulfid och svavel, men de kunde inte bli associerade med ett specifikt media. De årliga massorna av frigjorda metaller som släpps ut från området i ytvattnet är mellan 77-98 % högre än tillåtet av de etablerade riktlinjerna. Genom att separera vattnet som kan antas innehålla majoriteten av föroreningarna från det naturliga vattenflödet i avrinningsområdet kan volymen som behöver renas halveras. Eftersom föroreningen är så omfattande föreslås en kombination av åtgärdsmetoder; installation av gröna tak för att minska avrinningen från området, inneslutning av utfyllnadsmaterialet med bentonit och installation av ett filter för snabb, effektiv reduktion. För mer långsiktig rening föreslås det att optimera de existerande sedimentationsdammarna och våtmarken. Slutsatsen är att det kommer bli väldigt dyrt att åtgärda föroreningen på grund av dess omfattning, och hantering av sulfidförande berg för exploateringssyfte borde vara lagstadgat för att undvika miljömässiga och ekonomiska kostnader.

As the UN summit in September 2015 addressed with the Sustainable Development Goals (SDG), our planet faces great challenges.[1] Not only since then has the role of synthetic materials chemistry been discussed in this context.[2–16] This not only concerns the development of new materials with outstanding properties such as catalysts, materials for energy conversion, and cost-efficient energy converting and storage materials, but also a reduction of the energy consumption of established functional material syntheses. Therefore, new approaches addressing the three main categories to promote the potential for energy and resource efficiency have been proposed: lowering the temperature of the synthetic processes, improving the yield and purity of the materials, and reducing the amount of waste materials. In this context a number of low-temperature processes have been established, in which mainly solvents, i.e. amines and alcohols, are used in combination with previously synthesised precursors as the solubility of the starting materials limits their usability and most elements are not soluble in these solvents. Novel solvents like ionic liquids (ILs) showcase growing interest as they are considered particularly resource-efficient.[17,18] ILs are defined as liquids that are comprised entirely of ions, with melting points below 100 °C. Continuing on from the reported work in this field, this thesis focuses on investigating the ability of ILs in the syntheses for known chalcogenides at lower temperatures and the synthesis of new materials. The main focus lies on conversions with high atom economy, especially by starting from the elements and completely recycling the IL afterwards, and mechanistic studies elucidating the intermediate dissolved species. Furthermore, as imidazolium based ILs, and their derived LEWIS-acidic ILs [BMIm]Cl/nAlCl3 mixtures, have proven to be good crystallisation media in inorganic syntheses, and the class of mostly room-temperature liquid ILs (RTILs) based on phosphonium cations [P66614]Cl showcased the ability to dissolve red phosphorous, Pred, and the heavier chalcogens S, Se, and Te, this work mainly focuses on these two IL systems. This was also chosen as an in-depth understanding of the activation and resource-efficient synthesis of these chalcogenides has still not been established. As they are RTILs, they also made the characterisation of the reactive and dissolved species by liquid state NMR, Raman, UV/Vis spectroscopy and electrochemical characterisation possible. This expands the knowledge of which main group elements and ore-like starting materials can be used in ionothermal synthesis. As a starting point the thermoelectrically interesting materials class of tellurides is addressed. The under normal conditions hard to dissolve element tellurium readily dissolves in phosphonium ILs with the cations [P66614]+ and [P4444]+. In ILs with carboxylate anions a deep purple hue of the IL already occurred by dissolving tellurium at temperatures of 60 °C. Investigations on the solutions in the acetate ILs revealed the formation of tellurium anions (Ten)2– with chain lengths up to at least n = 5, which are in a dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an IL reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. However, the spectroscopic detection of tellurium cations in these solutions is difficult, but the coexistence of tellurium cations, such as (Te4)2+ and (Te6)4+, and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient in stabilizing both types of tellurium ions in solution.[19] In contrast, the acetate ILs show insufficient conversion in reactions of coin metals (Cu, Ag, Au) with tellurium to the corresponding tellurides, especially at low temperatures, however the chloride ILs successfully synthesise Cu2–xTe, CuTe, AuTe2 and Ag2Te. As the synthesis of the tellurides in neat ILs at temperatures down to 60 °C was only sufficient for the system Ag-Te, with a full conversion of the elements to Ag2Te, this was chosen as a model system for further investigations. Even at room temperature, a quantitative yield was achieved by using either 2 mol% of [P66614]Cl in dichloromethane or a planetary ball mill. The unexpected finding that phosphane-free [P66614]Cl also allows the quantitative synthesis of Ag2Te at 60°C implies an additional activation mechanism independent from the phosphane, which is yet unknown.[20] Subsequently, the manifoldly-used lighter chalcogen sulphur is tested for the synthesis of sulphides. Direct synthesis of binary sulphides of B, Bi, Ge, Mo, Cu, Au, Sn, In, Ti, V, Fe, Co, Ga, Ni, Al, Zn, and Sb in [P66614]Cl was tested at 100 °C, i.e. below the melting point of sulphur. Under these conditions, substantial sulphide formation occurred only for nickel (Ni3S4, Ni3S2, NiS) and copper (Cu2S, CuS). Sb showed no formation of crystalline sulphide, but after addition of EtOH, an orange material precipitated which was identified as amorphous metastibnite.[21] As generating these elements from their ores is highly energy consuming, direct dissolution experiments of the crystalline stibnite in [P66614][OAc] and Cl– were investigated and resulted in yellow solutions, from which the amorphous form can be precipitated upon exposure to EtOH air without any sign of decomposition of the IL. In particular, follow-up investigations were conducted on the solubility of Sb2S3 for follow-up chemistry in the LEWIS-acidic IL [BMIm]Cl · 4.7 AlCl3 at 160 °C which resulted in the formation of the novel chloride-terminated [Sb13S16Cl2]5+ quadruple-heterocubane cation-containing compound [Sb13S16Cl2][AlCl4]5.[21] Addition of CuCl in a slightly modified reaction resulted in the formation of the layered semiconductor Cu(Sb2S3)[AlCl4]. From this the AlCl3 can be leached by treatment with 0.1 molar hydrochloric acid, yielding a compound with the presumed composition Cu(Sb2S3)Cl.[22] As ILs showed to be able to activate elements that are insoluble in common solvents, and the formation of Sb2S3 from reactions mixtures of the elements raised the question of whether only the sulphur forms a mobile species or if antimony could additionally activated, the synthesis of binary antimony compounds directly from elements was explored as they are highly discussed as replacements for silicon-based semiconductors. Therefore the 12 elements Ti–Cu, Al, Ga, In, and Te, which are known to form binary compounds with Sb, were reacted with Sb in [P66614]Cl under inert conditions in a simple closed glass flask with vigorous stirring for 16 h at 200 °C. This resulted in the formation of NiSb, InSb, Cu2Sb and Sb2Te3. The applied reaction temperature is several hundred degrees below the temperatures required for solvent-free conversions. Compared to reactions based on diffusions in the solid state, reaction times are much shorter. The IL is not consumed and can be recycled. Since the reaction with Cu showed almost complete conversion, the influences of reaction time, temperature and medium were further investigated. In a diffusion experiment, Cu2Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. These systematic studies hence deliver a contribution to how ILs can help in the synthesis of new materials and how they can make a difference in the synthesis of inorganic materials as well in the context of “GREEN CHEMISTRY”. This can help in developing a more educated choice/toolbox of IL systems for reducing energy costs by reducing the temperature from high temperature inorganic syntheses to syntheses near room-temperature by using the elements as starting materials, with a high atom economy for the synthesis of known and new materials.

In this project, solid sulphur based Li3PS4 electrolytes doped with Li4SiO4 were synthesised using two methods. In method A, a bought β-Li3PS4 electrolyte from Nei Corp was doped with 5 mole per cent Li4SiO4, resulting in a glass-ceramic electrolyte. In method B, the electrolyte was synthesised using 5Li4SiO4-95(75Li2S-25P2S5), resulting in a glassy material. In addition, a reference was synthesised using 75Li2S-25P2S5. Ball milling was the method of choice to dope the glass ceramic electrolyte and synthesise the glassy electrolyte. The dopant Li4SiO4 was synthesised using the chemicals SiO2 and Li2CO3. All samples were analysed using Raman, XPS, XRD, and EIS. In the end, it was found that doping the bought β-Li3PS4electrolyte with Li4SiO4 increased the ionic conductivity. While introducing Li4SiO4 to the glassy electrolyte lowered the ionic conductivity. The increase in ionic conductivity in the glass ceramic electrolyte was partly attributed to the increase in amorphous content, which happened when it was ball-milled and suppressed P-S-P bonds. The decrease in ionic conductivity that happened when doping the glassy material, is most likely caused by residual Li2S that seems unable to react due to the dopant.

<p>Anodic protection has shown to be a viable method for reducing corrosion rates of stainless steels over a wide range of temperatures and is used to protect equipment in H₂SO₄ manufacturing. While effective at controlling corrosion in H2SO4 manufacturing, Impressed Current Anodic Protection (ICAP) systems have shown to have a number of issues. They require a constant source of current to ensure reliable corrosion protection; are relatively complex systems and expensive to install; improper potential control can lead to loss of corrosion protection; and some issues with cathode fouling and erosion have been reported. Galvanic Coupled Anodic Protection (GCAP) systems have not been widely utilized in industry, but offer some solutions to these issues. GCAP systems have been developed using Pt and Au as the cathode materials for use in H2SO4. Previous work on the oscillatory behaviour of austenitic stainless steels indicates that nickel sulphide (NiS) could be used as cathode material in a GCAP system in concentrated H₂SO₄ to protect stainless steel. The objective of this study was to develop a better understanding of the behaviour of NiS when galvanically coupled to Type 430 stainless steel to determine whether it can be used in a GCAP system. NiS and NiS(Ni) electrodes are able to provide the Icrit needed to passivate Type 430 at anode/cathode ratios of 10:1, while NiS(Ni) electrodes were able to provide the Icrit needed to passivate the Type 430 stainless steel at a ratio of 20:1. In addition it was shown that the NiS(Ni) electrode was able to maintain passivity of the Type 430 stainless steel array using an anode/cathode surface area ratio of 100:1. NiS was shown not to be inert in concentrated H₂SO4 and corrosion rate calculated via Tafel extrapolation and shown to be 0.014 mm/yr at room temperature and 0.128 mm/yr at 60 ºC.</p> / Master of Applied Science (MASc)

Semiconductors such as CuInGaSe2 and CdTe have been investigated as absorber layer materials for thin film solar cells since their band gap matches with the solar spectrum. Films as thin as 2m are sufficient for the absorption of the visible part of solar radiation, because they are characterized by a high absorption coefficient. However, the scarcity and high costs of Indium, Gallium and Tellurium have led to concerns on the sustainability of these technologies. The semiconductor Cu2ZnSnS4 (Copper Zinc Tin Sulphide) consisting of abundantly available elements promises to be an excellent photovoltaic absorber material. The present study is focused on the growth and characterization of CZTS/ZnS thin film heterostructure suitable for PV applications. Ultrasonic Spray Pyrolysis (USP), a variation of Spray Pyrolysis is a thin film deposition technique where the solution to be sprayed is atomized by ultrasonic frequencies. The details of the USP experimental set up and the deposition principle are presented in the thesis. The active layers of the solar cell, viz. the CZTS absorber layer and ZnS emitter layer were grown by this technique. The metal top contact was deposited using e-beam evaporation. The effects of copper concentration and sodium diffusion on the Cu2ZnSnS4 film properties were investigated. The films have shown preferred orientation along (112) direction confirming kesterite structure. The optical studies revealed that a reduction of copper in the films will bring the band gap energy to 1.5eV, which will match with the solar spectrum. Sodium diffusion in the CZTS films is found to passivate the grain boundaries and enhance the electrical conductivity. These properties render CZTS films as good photovoltaic absorber layers. ZnS has a high band gap and is non toxic unlike CdS. The influences of variation in substrate temperature and spray duration on the ZnS film properties were examined. The optical studies conducted on ZnS films revealed that they are highly transparent in the visible region of the solar spectrum. The films were found to possess a band gap of 3.5 eV. These properties make them potential candidates as solar cell emitter layers. The CZTS/ZnS heterojunction solar cell was fabricated and subjected to electrical characterization in dark and illuminated conditions. A conversion efficiency of 1.16% was achieved for the device.