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A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. August 2014. / The Central African Copperbelt is located in the Lufilian Arc which straddles the border between Zambia and the Democratic Republic of Congo (DRC). Mineralisation of the cupriferous Arc is found in basal Neoproterozoic Katangan Supergroup sedimentary rocks, which in DRC are termed the Mines Series Subgroup. The Mines Series is divided into the dolomitic and carbonaceous GRAT, DStrat RSF, RSC, SD and CMN units. The composition of the units is homogeneous across the Lubumbashi district and potentially across the Katangan basin. This study focussed on the Kinsevere and Ruashi deposits in the Lubumbashi district, which are approximately 50 km apart. The study confirmed that relative eustatic sea level changes resulted in the non-deposition of the RSF and RSC stratigraphic units at Kinsevere. Sedimentation was followed by early pervasive potassic alteration and silicification at the diagenetic stage whilst a magnesian dolomitisation event resulted in alteration of potassic feldspars and recrystallisation of carbonates. Albitisation was veincontrolled and late-stage scapolitisation altered evaporitic nodules. Finally, haematisation by late iron-rich fluids circulating through the Roan Group strata resulted in oxidation of sulphides. The structural analysis of Kinsevere Central pit indicates E-W and N-S shortening whereas the Ruashi pit 1 deposit underwent NE-SW and N-S shortening. Initial shortening, associated with Kolwezian deformation (D1), resulted in the formation of NE-thrust folds and a primary set of joints. The Kolwezian deformation event (D2), reoriented the shortening direction from E-W to N-S, creating interference folds and possibly a second set of joints. The final phase in the structural evolution of the Kinsevere and Ruashi deposits was late-stage brittle deformation (faulting). Mineralisation was a multi-stage process. Disseminated chalcopyrite and carrollite were deposited from formation waters during diagenesis in a stable basin environment. Chalcopyrite, carrollite, chalcocite and bornite are predominantly located at the base of the DStrat, whereas chalcopyrite and pyrite dominate the stratigraphically higher portions of the deposits. Hypogene vein mineralisation began at the syn- to late- orogenic stage with carrollite and chalcopyrite in beddingparallel veins. Possible changes in the compression direction created the perpendicularly oriented veins that host chalcopyrite, carrollite, bornite, covellite, digenite and chalcocite. Finally a late stage of chalcopyrite and pyrite deposition occurred in and around the evaporites, indicating a strong correlation between mineralisation, evaporites and scapolitisation. iii Near-surface supergene alteration of hypogene sulphide ores, resulted in Cu-Co carbonates and oxides, such as malachite, azurite, cobaltiferous malachite, chrysocolla, kolwezite and sphaerocobaltite being deposited in vugs and pore spaces above the meteoric water line. Faulted and brecciated zones tend to have deeper supergene alteration. Between the sulphide facies at depth and the supergene oxide facies at surface is a transition zone which marks the depth to which oxidation has penetrated. Sulphur isotope analysis from the Kinsevere and Ruashi deposits suggests a sulphur contribution from a continental Red-Bed sedimentary source and from an evaporitic source.

No description available.

The purpose of this study was to investigate the synthesis and properties of oxyaluminum pillared montmorillonites prepared using the controlled hydrolysis of aluminum isopropoxide as the source of pillaring species and to evaluate pillared montmorillonites as supports for hydrodesulfurization (HDS) catalysts. Several synthesis schemes were evaluated for the preparation of pillared montmorillonites. Successful pillaring was accomplished by addition of cyclohexane solutions of aluminum isopropoxide to aqueous montmorillonite suspensions. The pillared montmorillonite preparation was optimized for maximum interlayer spacing by variation of experimental parameters. Samples were characterized by x-ray diffraction and BET surface area. After dehydration a maximum interlayer spacing of approximately 6 A was obtained. As the ratio of aluminum isopropoxide to clay increased the surface area decreased. The interlayer limit was attributed to the primary pillaring species being a plate-like oxyaluminumcation having a boehmite layer structure whose thickness was about 6.1 A. Decreasing surface area for increasing aluminum to clay ratio probably resulted from exchange of larger cationic oxyaluminum plates into the interiayer volume. It was suggested that at the limit of very low surface area with a layer separation of about 6 A, the montmorillonite-oxyaluminum material consisted of alternating montmorillonite and 'boehmitem layers. / Ph. D.

A dissertation submitted to the Faculty of Science, University of Witwatersrand, in fulfilment of the requirements for the degree of Masters of Science Johannesburg, 2012. / Amplified loads of sulfate and nitrate have caused increased stress on soil systems in many areas of the world, as both are dominant components of acid rain. This is a critical environmental stress due to the damage caused to soil, water quality and ecosystem functioning. Issues concerning the rising emissions of these elements from local industries have begun to attract increasing attention in South Africa, as the rates of deposition in the Mpumalanga Highveld region alone is comparable to those experienced in First World countries. This study sought to investigate the use of natural stable isotopes of sulfur and nitrogen to identify the process transformations that these species undergo in environmental cycles. Total δ34S, δ15N and δ13C isotope signature of soils in the Mpumalanga region were combined with total elemental concentrations to determine the effect of deposition on the soil system. Soil samples from two soil depths (0 – 10 cm and 20 – 40 cm) were taken along a distance gradient from an identified pollution source, the Majuba power station. Long-term air quality data from the study area were also obtained from Eskom’s air quality monitoring stations, as well as sulfur and nitrogen deposition data from selected literature. Elemental concentrations decreased with soil depth as expected, while sites located approximately 25 km downwind of the power station were seen to contain higher concentrations of both soil sulfur and nitrogen. The mean per site soil sulfur concentration across all depths ranged from 0.009 % to 0.048 %, while the mean per site nitrogen concentration across all depths ranged from 0.056 % to 0.346 %. The mean soil carbon concentration in the top-soils ranged from 0.97 % to 7.93 %, and decreased in the sub-soils to 0.490 % to 3.270 %.The mean δ34S value for the top-soils was found to be 8.28 ‰ and increased to 10.78 ‰ in the sub-soils. Soil δ15N also increased with soil depth from 6.55 ‰ to 8.28 ‰. Soil δ13C values were seen to increase from -12.83 ‰ in the top-soils to -11.90 ‰ in the sub-soils. Lighter δ34S values at the surface may be due to anthropogenic deposition. The positive δ34S shift was attributed to a two-source mixing model (atmospheric deposition and bedrock) and isotopic fractionation processes that occur within the soil profile. The δ15N values of the top-soil were higher than what is expected if all nitrogen was derived from atmospheric nitrogen gas fixation. The increase in δ15N with depth suggested that isotope fractionation occurred during nitrogen export due to the faster reaction rate of 14N compared to 15N. The soil δ13C values indicated a typical C4 grassland system. New carbon at the top-soil depths was enriched in 13C due to the slower decay of 13C-depleted lignin; whereas in the sub-soils microbial recycling of carbon dominates and explained the higher 13C content of the older carbon. The conceptual framework presented for this project involves simultaneous processes of deposition and export in the soil system. This was particularly true for sulfur, where sites with lower isotope values had lower soil sulfur concentrations and vice versa. This indicates that high levels of deposition correspond to high net export. The sulfur and nitrogen isotopic signatures could not be used to as a direct means of source identification; however, the effectiveness of isotopes in elucidating transfer of these nutrients in the soil system was illustrated.

Héritées de l’atmosphère primitive, des anomalies dans les abondances relatives des isotopes du soufre (32S, 33S, 34S et 36S) sont enregistrées dans les sédiments terrestres d’il y a plus de 2,5 milliards d’années (i.e. archéens). Nous évaluons ici la robustesse des isotopes du soufre à tracer le recyclage précoce de croûte océanique et de sédiments, transférés dans le manteau profond ou stockés dans le manteau lithosphérique depuis la mise en place de la subduction. En Sibérie, le manteau lithosphérique a été naturellement échantillonné par l’éruption de la kimberlite d’Udachnaya-Est. Extrêmement bien préservée, riche en Na, K, Cl, S et contenant des reliques de croûte océanique Archéenne, cette kimberlite nous permet de tester : (1) l’hypothèse du recyclage de soufre atmosphérique Archéen dans le manteau lithosphérique et/ou la source de cette kimberlite ; (2) la cohérences entre les méthodes in situ (SIMS dans les minéraux de sulfure) et bulk (extraction chimique du soufre et spectrométrie de masse à source gazeuse) pour les mesures multi-isotopiques du soufre. Nos résultats, complétés par des mesures isotopiques en Rb-Sr, Sm-Nd et plomb (204Pb, 206Pb, 207Pb, 208Pb), montrent que : (1) les sulfates de la kimberlite et des nodules composés de chlorure-carbonate ont une origine magmatique profonde, non-contaminée par les sédiments encaissants, suggérant la présence de domaines oxydés et riches en sulfates dans le manteau ; (2) les mesures isotopiques du soufre par méthode bulk sont cohérentes avec les populations de sulfures observées in situ ; (3) les sulfures des kimberlites salées sont appauvris en 34S par rapport à la valeur chondritique et enregistrent de faibles anomalies isotopiques en soufre ; (4) les péridotites déformées contiennent d’autres sulfures appauvris en 34S, qui eux préservent des anomalies en 33S et 36S héritées de la surface archéenne, malgré un équilibrage isotopique du chronomètre U-Pb lors de l’éruption de la kimberlite / Inherited from the early atmosphere, anomalies in the relative abundances of sulfur isotopes (32S, 33S, 34S and 36S) are recorded in sediments older than 2.5 billion year (i.e. Archean). Here we test the robustness of sulfur isotopes to trace the early recycling of oceanic crust and sediments that may have been transferred to the deep mantle or stored in the lithospheric mantle since the onset of subduction. In Siberia, the lithospheric mantle has been naturally sampled by the Udachnaya-East kimberlite while it was erupting. Because it is extremely well preserved, rich in Na, K, Cl, S and contains remnants of oceanic crust recycled during the Archean, this kimberlite enables us to test : (1) the hypothesis of an early recycling of Archean atmospheric sulfur in the lithospheric mantle and/or the deeper source of the kimberlite; (2) the coherence between in situ (SIMS in sulfide minerals) and bulk methods (chemical extraction of sulfur from powdered rocks, followed by gas source mass-spectrometry) for measuring multiple sulfur isotopes. Our results, combined with measurements of Rb-Sr, Sm-Nd and lead (204Pb, 206Pb, 207Pb, 208Pb) isotopes, show that: (1) sulfates from the Udachnaya-East kimberlite and its nodules composed of chloride-carbonate have a deep, magmatic origin, uncontaminated by host sediments, suggesting the presence of sulfate-rich, oxidized domains in the mantle; (2) measurements of sulfur isotopes by bulk methods are consistent with the sulfide populations observed in situ; (3) sulfides from salty kimberlites are depleted in 34S with respect to the chondritic value and record small anomalies in sulfur isotopes ; (4) sheared peridotites contain another population of sulfides that are depleted in 34S and preserve 33S and 36S anomalies inherited from the Archean surface, despite resetting of the U-Pb chronometer during kimberlite eruption

Esta memoria trata de la evolución geoquímica de cuencas evaporíticas terciarias y de su utilidad en la reconstrucción de la evolución isotópica (delta(34)S y delta(18)O) del sulfato disuelto en el océano durante el Terciario. Para ello se ha dividido el texto en tres partes principales: Parte 1. Se tratan los aspectos metodológicos y se describen las técnicas empleadas. El microanálisis de inclusiones fluidas mediante Cryo-SEM-EDS, permite el análisis cuantitativo de los solutos en inclusiones fluidas congeladas de tamaños de hasta 15 delta m. Los electrolitos analizados son los componentes mayoritarios presentes en las salmueras atrapadas. Na, K. Mg, Ca, Cl y SO(4). La precisión del método varia según los casos, pero es inferior al 6% para todos ellos salvo para el Cl (<15%). Con el objeto de ampliar el número de elementos analizados a minoritarios y traza, se han realizado análisis mediante otra técnica, LA-ICP-MS, demostrándose que ambas técnicas son complementarias. También se describe la metodología empleada en el análisis isotópico, en especial el funcionamiento de las líneas de extracción de gases y la manipulación de las muestras. Otra parte fundamental es la descripción del funcionamiento de las simulaciones numéricas y sus fundamentos teóricos. Todos los datos analíticos obtenidos de forma sistemática a lo largo de las secuencias evaporíticas son comparados con simulaciones numéricas en diferentes escenarios. Estas comparaciones permiten refinar un modelo de evolución de las cuencas evaporiticas durante la precipitación de las evaporitas, en especial de las halitas. De esta forma se obtienen los parámetros fundamentales en la evolución hidrológica de la cuenca: el índice de restricción, que indica lo abierta o cerrada que está la cuenca a los aportes externos, y las proporciones de recarga, que son las proporciones aproximadas de los distintos tipos de aguas que llegan a la cuenca (continentales, marinas, reciclajes, etc.). Las composiciones isotópicas también están introducidas en los modelos, de forma que una vez determinados el índice de restricción y las proporciones de recarga puede ajustarse la evolución isotópica de las unidades evaporíticas. Al establecerse el carácter marino de la totalidad o de parte de las unidades, éstas pueden ser utilizadas para deducir la composición isotópica de las salmueras y del océano original del que proceden. Los datos de composición isotópica del mar, obtenidos a partir de estas unidades están corregidos de los fraccionamientos provocados por cristalización o por variaciones en el índice de restricción de la cuenca. Por otra parte pueden detectarse otros fenómenos que modifican la composición isotópica, tales como la sulfato-reducción bacteriana o el reciclaje de evaporitas previamente formadas. En el caso del reciclaje puede llegar a cuantificarse de forma aproximada. Parte II. En esta parte se aplica la metodología descrita a diferentes cuencas evaporíticas. a) Cuenca surpirenaica (subcuenca navarra). En este caso ya existen trabajos anteriores en los que se aplica la metodología descrita y en los que se muestra el carácter marino de la unidad halítica inferior (UHI) y el carácter continental de la unidad halítica superior (UHS). En esta memoria se aplica de forma complementaria el estudio de inclusiones fluidas al estudio de las zonas estériles en los yacimientos de silvita de Subiza (Navarra). Se determina el carácter primario de la silvita y el origen sinsedimentario de las zonas estériles. b) Cuenca surpirenaica (subcuenca catalana). Ésta tiene apones fundamentalmente marinos, si bien se pone de manifiesto la importante influencia del reciclaje de los yesos marginales durante la precipitación de la halita. Esta influencia queda registrada en las composiciones isotópicas más pesadas de la subcuenca catalana respecto de la navarra. Ambas subcuencas siguen una evolución paralela, aunque la mayor influencia continental en la subcuenca catalana parece sugerir una menor conexión entre ambas subcuencas. Para ambas subcuencas se deduce la composición isotópica del mar durante el Eoceno superior. c) Fosa Renana (Cuenca de Mulhouse. Alsacia). La evolución de esta cuenca durante la precipitación de la Sal IV es fundamentalmente continental como indican la evolución de solutos en las inclusiones fluidas, composiciones isotópicas y determinaciones (87)Sr/(86)Sr. Es posible la existencia de una influencia marina en la base de la Sal IV, cerca de la llamada zona fosilífera, si bien no se preserva según evoluciona el medio. En esta cuenca se ponen de manifiesto procesos de mezclas de aguas de diferentes orígenes y en proporciones variables en el tiempo. También se identifican procesos redox con reequilibración del oxígeno del sulfato con el oxígeno disuelto en la salmuera. Eslos procesos provocan el enriquecimiento de la delta(18)O hasta valores de +/- 22º/ºº y parecen estar relacionados a una mayor actividad bacteriana en la cuenca. Los datos obtenidos no permiten deducir la composición isotópica del mar durante el Oligoceno. d) Cuenca Precarpática. Se pone de manifiesto la importancia del reciclaje durante la precipitación de toda la unidad halitica. La fuente de solutos es mayoritariamente marina, al principio de la precipitación de halita, y se pone de manifiesto un incremento notable del reciclaje de evaporitas. La composición isotópica de los sulfatos intercalados entre halita y de los yesos marginales es muy semejante. Se plantea el reciclaje de los sulfatos precipitados en el margen activo de la cuenca como posible fuente de solutos. A partir de los datos obtenidos y una vez determinada la influencia del reciclaje, se deduce una composición isotópica para el mar durante el Badeniense. e) Cuenca de Lorca. Las conclusiones de los estudios preexistentes sobre inclusiones fluidas se ven confirmadas por los nuevos datos isotópicos obtenidos. Se diferencia en la unidad salina un tramo inferior de origen marino, con variaciones en el índice de restricción y apones continentales puntuales que provocan ligeras variaciones isotópicas. Por encima se distingue un tramo superior, de origen continental, con una evolución isotópica que se interpreta por el reciclaje de diferentes proporciones de sulfatos de la propia cuenca y sulfatos de origen Triásico. A partir de los datos de la unidad salina (tramo inferior) se deduce la composición isotópica del mar messiniense. f) Cuenca de Caltanissetta. Los datos de inclusiones fluidas preexistentes y los realizados para esta memoria diferencian un tramo halltico inferior, de origen marino, y un tramo superior, separado por sulfatos de K y Mg, que muestra su carácter marino, pero con influencias del reciclaje de evaporitas de la propia cuenca. Se ha determinado la evolución isotópica de dos sondeos diferentes, siendo los resultados iguales para ambos, y en concordancia con los resultados de las inclusiones fluidas. A partir del tramo marino se obtiene un rango para la composición isotópica delta(34)S del océano messiniense que coincide con la deducida en la cuenca de Lorca. Las delta(18)O obtenidas son aproximadamente +3 º/ºº más pesadas e incompatibles con las deducidas en Lorca. Se propone la existencia de procesos redox generalizados de forma semejante a como sucede en medios actuales de origen marino. Parte III. En esta parte se realizan diversas consideraciones sobre la evolución del sulfato disuelto en el océano. A partir de los datos obtenidos en diferentes cuencas evaporíticas, se concluye que el déficit de sulfato (respecto a la evaporación del mar actual), común a muchas cuencas evaporíticas, no se debe a cambios globales en la composición del océano sino a variaciones locales dentro de las propias cuencas evaporíticas. Procesos de dolomitización o la entrada de salmueras ricas en Ca son las responsables del descenso en la concentración de sulfato. Una de las consecuencias directas del déficit de sulfato es la precipitación de silvita como mineral primario a partir de la evaporación de agua marina. En cuanto a la composición isotópica., se insiste en la necesidad de conocer con exactitud el origen marino de las evaporitas empleadas para deducir la evolución isotópica del sulfato disuelto en el océano. La metodología empleada en trabajos anteriores en la que se utilizan evaporitas de orígenes diversos, y en ocasiones desconocidos, provocan la imprecisión de las curvas de evolución isotópica deducidas. La metodología presentada en esta memoria permite el refinamiento de dichas curvas y la obtención de datos precisos sobre la composición isotópica del sulfato disuelto en el océano. / The subject of this thesis is the geochemical evolution of tertiary evaporitic basins and their use in reconstructing the isotopic evolution (delta(34)S y delta(18)O) of sulphate dissolved in the ocean during the Tertiary. Part 1: The methodology is discussed and the techniques employed are described. Microanalysis using Cryo-SEM-EDS allows the quantitative analysis of frozen fluid inclusions up lo 15 mili-micres in size. The major solutes analysed from the trapped brine are Na. K, Mg, Ca, CI and SO. To analyse minor and trace elements, diverse analyses have been carried out using another technique, LA-ICP-MS. Thus demonstrating that, these techniques complement each other. The methodology used in isotopic analysis and numerical simulations, how they work and their theoretical bases are also described. The analytical data are compared with numerical simulations that reproduce different scenarios. Thus a model of the evaporitic basins evolution during precipitation can be refined. From these models fundamental parameters in the basins hydrological evolution have been obtained: restriction index and recharge proportions. The isotopic compositions are also introduced into the models so the isotopic evolution of the evaporitic units can be adjusted. Once the marine origin has been established, the model is used to deduce the brine's isotopic composition and that of the original ocean. Part II: In this section the methodology discussed above is applied to various evaporitic basins. - Southpyrenean basin (Navarran sub-basin, Spain) - Southpyrenean basin (Catalonian sub-basin, Spain) - Rhine Graben (Mulhouse basin, Alsace, France) - pre-Carpathian basin (Poland) - Lorca basin (Murcia, Spain) - Caltanissetta basin (Sicily, ltaly) Part III: According to the data obtained from different evaporitic basins it is concluded that the sulphate deficit - in respect to the evaporation of today's seawater - common in many evaporitic basins is not due to global changes in the oceans composition but rather lo local variations within the evaporitic basins. Regarding the isotopic compositions, it is important lo assure the exact marine origin of the evaporates that are used to deduce the isotopic evolution of sulphate dissolved in the ocean. The methodology presented in this thesis allows isotopic curves to be refined.

Algoma-type banded iron formation is common in Neoarchean greenstone belts, and many of its distinctive features such as the banding of iron-rich and silica-rich material and deposition in volcanic terranes have been ascribed to their deposition related to volcanic-hydrothermal activity and cyclic variability in depositional pathways. The work presented in this thesis tests these assumptions and presents a model for the deposition and post-depositional processes now represented by the petrography and geochemistry of a 2.73 Ga type-locality of Algoma-type BIF in Temagami, ON. Adsorption of components onto the surface of Fe-oxyhydroxides forming in the anoxic Neoarchean water column is the most likely process capable of transferring silica, as well as trace quantities of transition metals, rare earth elements, Ge, P, U and other components to the sediment. The petrogenesis of the Temagami BIF lithologies suggests ongoing recrystallization processes and volume loss reactions leading to the formation of magnetite layers, while jasper is identified as the most pristine lithology best representative of the initially deposited Fe-oxyhydroxide-silica gel. Recrystallization and volume loss reactions are controlled by the ongoing dewatering during compaction and diagenesis, without the influence of external hydrothermal or metamorphic fluids. When corrected for the volume loss and small amounts of clastic contamination, little residual variability can be observed in the composition of jasper and magnetite layers, indicative of an originally homogenous primary precipitate instead of sorted and layered material deposited on the seafloor. This model is in stark contrast to previous interpretations of seasonal variability in biologic activity, cyclical seasonal or hydrothermal events responsible for primary layering in BIF. Instead, very little direct input of hydrothermal components is recorded in the chemistry of the Temagami BIF, and elements abundant in high-temperature hydrothermal fluids such as sulfur are instead sourced from atmospheric sources and deposited by bacterial pathways. Lack of primary chemical variability and non-hydrothermally sourced components captured in BIF argue against a genetic link to local hydrothermal venting, but rather an open ocean depositional setting. As such, the Temagami BIF does not represent a marker horizon related to local or regional hydrothermal venting and potential formation of associated massive sulfide deposits but reflects processes and the chemistry of the open Neoarchean ocean.

No description available.