A research project submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science. / Rb-Sr emplacement ages of nineteen kimberlites from the Prieska Province vary from 74 to 174 Ma, Their isotopic, whole-rock geochemical signatures and perovskite REE distributions were also determined. Non-micaceous and micaceous kimberlites from the area show similar petrographic, geochemical and isotopic compositions relative to cratonic kimberlites, indicating similar sub-continental mantle source compositions in the two tectonic environments. Transitional varieties of kimberlite, which can be defined petrographically, geochemically and isotopically are also recognised from the area, but are not prevalent in the cratonic environment. The Prieska Province kimberlites are possibly derived by partial melting processes within a subcontinental reservoir characterised by a spectrum of compositions from time-averaged depleted (HllMU) to enriched (Group II). The occurrence of these components in both on- and off-craton settings indicates that the kimberlite source area is not strictly linked to the suberatonic lithosphere. Mantle' plume sources are not favoured because of the variable source compositions and distribution of emplacement ages within the Province. Transitional kimberlites were derived from a source component with mixed character, not yet noted from within the Kaapvaal Craton. This is the first documented example of isotopically transitional kimberlites from southern Africa. / AC2017

Ce travail de thèse a appréhendé les mécanismes de stockage/libération, d’un point de vue élémentaire et isotopique, du calcium (Ca) et du strontium (Sr) sur ou dans des phases minérales communes des sols (minéraux primaires, minéraux argileux, oxy-hydroxydes, carbonate pédogénétiques). Une méthode de mesure robuste du δ88Sr a dû être développée et validée par la mesure de matériaux de références internationaux, pour la plupart jamais mesuré dans la littérature. Les résultats montrent que l’adsorption du Ca sur des minéraux phyllosilicatés génère un fractionnement isotopique par prélèvement préférentiel de l’isotope léger (40Ca) dans nos conditions expérimentales lorsque les minéraux possèdent une charge structurale et une surface spécifique importante et/ou un espace interfoliaire ouvert à l’adsorption de cations hydratés. Une étude sur des rhizolithes en milieu naturel a mis en avant que l’utilisation des isotopes du Ca et du Sr permet un traçage de source et de mécanismes efficaces dans les thématiques touchant au stockage de ces deux éléments dans les sols. / This PhD thesis examined the mechanisms of storage and release, from and elementary and isotopically point of view, of calcium (Ca) and strontium (Sr) onto or into mineral phases commonly encountered within soils (primary minerals, clay minerals, oxy-hydroxides, pedogenic carbonate). A robust δ88Sr measurements method had to be developed in the laboratory and validated by the measurement of international reference materials, mostly never measured in the literature. The results of this work show that Ca adsorption onto phyllosilicate minerals generates a quantifiable isotopic fractionation by preferential uptake of the light isotope (40Ca) under our experimental conditions when the minerals have a significant structural charge and specific surface area and/or an interlayer space open to hydrated cations adsorption. A study on rhizoliths in natural environment has also highlighted that the combination of Ca and Sr isotopes allows an effective tracing of sources and mechanisms in the problematic related to the storage of these two elements within soils.

A crescente importância da questão do uso sustentável da água e a conseqüente necessidade de se diminuir a poluição e o desperdício desse reservatório terrestre, impulsionaram esse estudo. O objetivo principal do trabalho é avaliar a aplicação de indicadores isotópicos ambientais, como Sr, Pb, O e D, para estudos da origem e qualidade da água de recarga de um aqüífero, bem como do impacto da impermeabilização da superfície da cidade sobre esses indicadores. Para isso foram escolhidas duas áreas na Bacia do Alto Tietê, na Cidade de São Paulo, uma na Zona Oeste (área 1 - USP) e outra na Zona Leste (área 2 - VE), onde foram coletadas amostras de água da SABESP, de água de chuva e de poços de monitoramento, por um ano, além de sedimentos. Foram realizadas análises químicas em 390 amostras de água e 62 de solos, além de 413 análises isotópicas de H e O e 122 de Sr e Pb em água, além de 34 de Sr e Pb em sedimento. A determinação de procedimentos químicoanalíticos, para análises isotópicas de Pb e Sr em águas com baixas concentrações destes elementos, foi o primeiro resultado deste trabalho e definiu que as amostras devem ser filtradas e acidificadas, antes da evaporação, e seus resíduos devem ser dissolvidos com HCl, HNO3 e HF, para depois a amostra ser purificadas por resina de troca iônica. Todas as amostras de água subterrânea apresentaram alguma contaminação antrópica. Os poços da VE apresentaram contaminação caracterizada por altas concentrações de cloreto, sulfato e nitrato e a USP de cloreto, sulfato, amônio, sódio e fluoreto, além de elevada alcalinidade. Os lixiviados de Pb em sedimentos mostraram que há pouca interação destes com a água subterrânea e esses não foram utilizados como membros finais da mistura. As análises isotópicas (H e O) das chuvas indicaram que as precipitações da Cidade de São Paulo sofrem influência tanto do efeito quantidade, quanto das diferentes origens de massas de ar em diferentes períodos do ano. A estimativa de recarga utilizando os isótopos mostrou que a VE, mais impermeável, apresentou uma contribuição antrópica 10% (H e O) a 20% (Pb) maior do que a USP. Na USP, a recarga natural calculada por isótopos de H e O possui uma média de 70%, enquanto na VE esse valor cai para 59%. Os isótopos de Pb forneceram médias de 53% e 35%, respectivamente para USP e VE, de recarga natural. Diante dos cálculos efetuados e análises (químicas e isotópicas) concluiu-se que os isótopos de Sr não são indicados para traçar a recarga de áreas contaminadas, já que mostram pouca interação entre a rocha e a água. Os isótopos estáveis não apresentaram muita diferença entre as assinaturas de água da SABESP e das amostras mais contaminadas por esgoto e não são bons diferenciadores dessas duas fontes. Já os isótopos de Pb são bons indicadores de recarga para áreas contaminadas, porque conseguem discriminar as águas oriundas de fugas da rede da SABESP e do esgoto. / The importance of a sustainable use of water and its resultant necessity of reducing groundwater pollution and waste is the driving force of this study. The main subject is to evaluate the application of environmental isotopes, as H, O, Sr and Pb, for studying the groundwater recharge sources and its quality, as well as the impact of the surface sealing on these indicators, due to urbanization. Two areas with different occupation in São Paulo City, within the Upper Tietê Watershed, one in west zone (area 1) and other in the east zone (area 2) were chosen to do this study. In both areas, water samples were collected for a year from: monitoring wells, supply agency and rain. Sediments were also sampled during drilling. Chemical analyses were carried out in 390 water samples and 62 sediments, whereas H and O isotopic analyses were performed on 413 water samples and Pb and Sr isotopic analyses on 122 water samples and 34 sediments. This work also determined that analytical procedures for Pb and Sr isotopic analyses of groundwater samples with low Sr and Pb concentration should filter and acidify water samples prior to evaporate it, their residue should be dissolved with HCl, HNO3 and HF, before purification by ionic exchange resin. All groundwater samples showed some anthropogenic contamination. Groundwater contamination in VE is characterized by high concentrations of Cl-, SO42- and NO3-, whereas in USP of Cl-, SO42-, NO3-, Na+ and F- besides high alkalinity. The Pb leaching isotopic technique applied on sediments showed that there is low water-rock interaction and they were not used as end members for the mixing calculation. The H and O isotopic analyses indicated that precipitation in São Paulo are dependent of the amount effect and the different sources of air masses in different climate periods. The isotopic estimate of recharge indicated that VE, which has a more impermeable surface, has approximately 10% (H e O) to 20% (Pb) more anthropogenic recharge than USP. At USP the natural recharge calculated by H and O isotopes has mean value of 70%, whereas in VE this value drops to 59%. The Pb isotopes indicated a natural recharge of 53% and 35% for USP and VE, respectively. The conclusions made with the isotopic and chemical results are that: Sr isotopes are not good recharge tracers for contaminated areas with low residence time; O and H isotopes do not present significant differences between isotopic signatures from water distributed by the public supply company and most contaminated samples by sewage; Pb isotopes are good indicators of recharge tracers for contaminated areas, as they can discriminate waters from sewer leakage and public supply company waters.

by Ho Kai Wing Kevin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 94-98). / ABSTRACT --- p.iv / ACKNOWLEDGEMENTS --- p.vi / Chapter CHAPTER ONE: --- INTRODUCTION --- p.1 / Chapter 1.1 --- Basic Co-NMR Theory --- p.1 / Chapter 1.2 --- Method Employed --- p.5 / Chapter 1.2.1 --- Solvent Dependent Studies on Cobalt(III) complexes using 59Co NMR Spectroscopy --- p.5 / Chapter 1.2.2 --- Relationship between δiso and NQCC of Cobalt(III) Complexes in Solid --- p.7 / Chapter 1.3 --- Donor Acceptor Interactions --- p.8 / Chapter 1.4 --- Objectives of this Thesis --- p.10 / Chapter CHAPTER TWO: --- EXPERIMENTAL --- p.11 / Chapter 2.1 --- Synthesis --- p.11 / Chapter 2.2 --- NMR Measurements --- p.13 / Chapter 2.2.1 --- 59Co NMR Measurements --- p.13 / Chapter 2.2.2 --- 13c NMR Measurements (T1 Measurements) --- p.14 / Chapter 2.3 --- Viscosity Measurements --- p.15 / Chapter 2.4 --- UV-Vis Spectral Measurements --- p.15 / Chapter CHAPTER THREE --- 59Co NMR STUDY OF MAGNETIC COBALT(III) COMPLEXES --- p.16 / Chapter 3.1 --- Solvent-Dependent Studies of Cobalt(III) Complexes --- p.16 / Chapter 3.1.1 --- "Study of [Co(en)3]Cl3 and cis, trans-[Co(en)2(N3)2]NO3" --- p.17 / Chapter 3.1.2 --- Study of trans- [Co(en)2(NH3)2]Cl3 and trans- [Co(en)2(N02)2]NO3 --- p.29 / Chapter 3.1.3 --- "Study of trans- Na[Co(acac)2 (N02)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I" --- p.36 / Chapter 3.1.4 --- Summary --- p.48 / Chapter 3.2 --- "Simultaneous Determination of CSA, ic, and NQCC of Cobalt(III) complexes in Different Solvents" --- p.49 / Chapter 3.2.1 --- Method --- p.49 / Chapter 3.2.2 --- "Study of trans- Na[Co(acac)2(N02)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I and trans-[Co(acac)2(MeNH2)2]I" --- p.52 / Chapter 3.2.3 --- Study of trans- [Co(en)2(N〇2)2]N03 and trans- [Co(en)2(NCS)2]NCS --- p.58 / Chapter 3.2.4 --- Study of trans- [Co(en)2(NH3)2]Cl3 and trans- [Co(en)2(N3)2]NO3 --- p.63 / Chapter 3.2.5 --- Summary --- p.68 / Chapter 3.3 --- Resolution of the d-d Electronic Transition Energies in Cobalt Complexes and its Application to the Donor-Acceptor Interactionsin Cobalt Complexes - Application of Equation 3.3.1 --- p.70 / Chapter 3.3.1 --- Method --- p.70 / Chapter 3.3.2 --- "Study of trans- [Co(en)2(N02)2]N03,trans- [Co(en)2(NCS)2]NCS, trans- [Co(en)2(N3)2]N03 and trans- [Co(en)2(NH3)2]Cl3" --- p.72 / Chapter 3.3.3 --- "Study of trans- Na[Co(acac)2(NO2)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I" --- p.86 / Chapter CHAPTER FOUR --- CONCLUSION AND FUTURE WORKS --- p.92 / REFERENCES --- p.94

A crescente importância da questão do uso sustentável da água e a conseqüente necessidade de se diminuir a poluição e o desperdício desse reservatório terrestre, impulsionaram esse estudo. O objetivo principal do trabalho é avaliar a aplicação de indicadores isotópicos ambientais, como Sr, Pb, O e D, para estudos da origem e qualidade da água de recarga de um aqüífero, bem como do impacto da impermeabilização da superfície da cidade sobre esses indicadores. Para isso foram escolhidas duas áreas na Bacia do Alto Tietê, na Cidade de São Paulo, uma na Zona Oeste (área 1 - USP) e outra na Zona Leste (área 2 - VE), onde foram coletadas amostras de água da SABESP, de água de chuva e de poços de monitoramento, por um ano, além de sedimentos. Foram realizadas análises químicas em 390 amostras de água e 62 de solos, além de 413 análises isotópicas de H e O e 122 de Sr e Pb em água, além de 34 de Sr e Pb em sedimento. A determinação de procedimentos químicoanalíticos, para análises isotópicas de Pb e Sr em águas com baixas concentrações destes elementos, foi o primeiro resultado deste trabalho e definiu que as amostras devem ser filtradas e acidificadas, antes da evaporação, e seus resíduos devem ser dissolvidos com HCl, HNO3 e HF, para depois a amostra ser purificadas por resina de troca iônica. Todas as amostras de água subterrânea apresentaram alguma contaminação antrópica. Os poços da VE apresentaram contaminação caracterizada por altas concentrações de cloreto, sulfato e nitrato e a USP de cloreto, sulfato, amônio, sódio e fluoreto, além de elevada alcalinidade. Os lixiviados de Pb em sedimentos mostraram que há pouca interação destes com a água subterrânea e esses não foram utilizados como membros finais da mistura. As análises isotópicas (H e O) das chuvas indicaram que as precipitações da Cidade de São Paulo sofrem influência tanto do efeito quantidade, quanto das diferentes origens de massas de ar em diferentes períodos do ano. A estimativa de recarga utilizando os isótopos mostrou que a VE, mais impermeável, apresentou uma contribuição antrópica 10% (H e O) a 20% (Pb) maior do que a USP. Na USP, a recarga natural calculada por isótopos de H e O possui uma média de 70%, enquanto na VE esse valor cai para 59%. Os isótopos de Pb forneceram médias de 53% e 35%, respectivamente para USP e VE, de recarga natural. Diante dos cálculos efetuados e análises (químicas e isotópicas) concluiu-se que os isótopos de Sr não são indicados para traçar a recarga de áreas contaminadas, já que mostram pouca interação entre a rocha e a água. Os isótopos estáveis não apresentaram muita diferença entre as assinaturas de água da SABESP e das amostras mais contaminadas por esgoto e não são bons diferenciadores dessas duas fontes. Já os isótopos de Pb são bons indicadores de recarga para áreas contaminadas, porque conseguem discriminar as águas oriundas de fugas da rede da SABESP e do esgoto. / The importance of a sustainable use of water and its resultant necessity of reducing groundwater pollution and waste is the driving force of this study. The main subject is to evaluate the application of environmental isotopes, as H, O, Sr and Pb, for studying the groundwater recharge sources and its quality, as well as the impact of the surface sealing on these indicators, due to urbanization. Two areas with different occupation in São Paulo City, within the Upper Tietê Watershed, one in west zone (area 1) and other in the east zone (area 2) were chosen to do this study. In both areas, water samples were collected for a year from: monitoring wells, supply agency and rain. Sediments were also sampled during drilling. Chemical analyses were carried out in 390 water samples and 62 sediments, whereas H and O isotopic analyses were performed on 413 water samples and Pb and Sr isotopic analyses on 122 water samples and 34 sediments. This work also determined that analytical procedures for Pb and Sr isotopic analyses of groundwater samples with low Sr and Pb concentration should filter and acidify water samples prior to evaporate it, their residue should be dissolved with HCl, HNO3 and HF, before purification by ionic exchange resin. All groundwater samples showed some anthropogenic contamination. Groundwater contamination in VE is characterized by high concentrations of Cl-, SO42- and NO3-, whereas in USP of Cl-, SO42-, NO3-, Na+ and F- besides high alkalinity. The Pb leaching isotopic technique applied on sediments showed that there is low water-rock interaction and they were not used as end members for the mixing calculation. The H and O isotopic analyses indicated that precipitation in São Paulo are dependent of the amount effect and the different sources of air masses in different climate periods. The isotopic estimate of recharge indicated that VE, which has a more impermeable surface, has approximately 10% (H e O) to 20% (Pb) more anthropogenic recharge than USP. At USP the natural recharge calculated by H and O isotopes has mean value of 70%, whereas in VE this value drops to 59%. The Pb isotopes indicated a natural recharge of 53% and 35% for USP and VE, respectively. The conclusions made with the isotopic and chemical results are that: Sr isotopes are not good recharge tracers for contaminated areas with low residence time; O and H isotopes do not present significant differences between isotopic signatures from water distributed by the public supply company and most contaminated samples by sewage; Pb isotopes are good indicators of recharge tracers for contaminated areas, as they can discriminate waters from sewer leakage and public supply company waters.

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Uranium and thorium isotopes are powerful and sensitive tracers of a wide range of oceanographic and environmental processes. This thesis makes use of these isotopes in deep sea sediments to reconstruct dust fluxes and deep ocean respired carbon storage over the last 350 kyr in the central equatorial Pacific. The paleoenvironmental information obtained through the application of these isotopes as proxies reveals important information about the Earth’s ocean and atmosphere, and their connectivity on millennial and glacial-interglacial timescales. In Chapter 1 of this thesis I introduce the proxies and principals employed in our paleoenvironmental reconstructions. Subsequently, the first section of this thesis explores the use of 230Thxs,0-derived 232Th fluxes as a proxy for aeolian dust deposition at three sites beneath the shifting Pacific Intertropical Convergence Zone (ITCZ). The new records presented here improve upon existing records of tropical Pacific dust fluxes by increasing the temporal resolution ~5 fold and adding almost an order of magnitude more data. Specifically, we reconstruct dust fluxes in two cores from 0-150 ka and from one core from 0-350 ka In addition to substantially improving constraints on tropical dust fluxes this work also utilizes the spatial transect of cores to infer past positions of the ITCZ on glacial-interglacial and millennial timescales. This proxy approach to reconstruct ITCZ position has only been applied and published once previously, in a relatively low-resolution study. Chapter 2, entitled “Large deglacial shifts of the Pacific Intertropical Convergence Zone,” presents evidence that the Pacific ITCZ experienced large shifts in latitudinal position, on millennial timescales during the penultimate deglaciation. The data resolve abrupt shifts in atmospheric circulation associated with deglaciation, in this case Termination II, at the boundary between the full glacial marine isotope stage (MIS) 6 and the peak interglacial MIS 5. These shifts are significant in that they appear to have occurred at the same time as changes in the North Atlantic driven by Heinrich Stadial 11 and may have played an important role in pushing the climate system over the threshold for deglaciation. Indeed, this study is the first to show evidence of a millennial-scale ITCZ response at the time of the Heinrich Event 11 catastrophic iceberg discharge event. Additionally, the data point to the existence of a previously unidentified millennial peak in northern hemisphere dust abundance during the penultimate deglaciation. In Chapter 3, “Climate-related response of dust flux to the central equatorial Pacific over the past 150 kyr,” records of dust flux are used to provide strong evidence for an association between high latitude stadial events and tropical dust fluxes during the last 150 kyr. These high-resolution observations permit the drawing of conclusions about the meridional location of the Pacific ITCZ during six Greenland stadials. As with the shift of the ITCZ during Heinrich Stadial 11, these events were associated with perturbations of the interhemispheric thermal gradient and coincident movement of the ITCZ presents an important constraint on the sensitivity of the tropical atmosphere to high latitude perturbations. The conclusions stemming from the interpretation of geochemical and paleoceanographic data presented in Chapters 2 and 3 are of broad relevance to a variety of geoscience disciplines that seek an understanding of the climate system. For example, these results confirm predictions made by modeling studies about the response of the ITCZ to high latitude climate forcing and provide an important new set of boundary conditions for modeling studies aimed at reconstructing changes in insolation forcing and tropical hydroclimate. The results show that paleo-reconstructions can constrain the magnitude of even abrupt ITCZ movement, demonstrating the potential to relate ITCZ changes to the magnitude of thermal forcing and to investigate thermal and hydrological components of other climate change events, past and future. Additionally, these results help improve understanding of the relationship between atmospheric dust abundance and climate, with implications for planetary albedo and micronutrient fertilization of the oceans. The second portion of this thesis focuses on using authigenic uranium (aU) to reconstruct deep water chemistry with implications for paleocirculation. Chapter 4, “Repeated storage of respired carbon in the equatorial Pacific Ocean over the last three glacial cycles,” presents evidence that the Pacific was a significant reservoir for respired carbon during glacial periods over at least the last 350 kyr. This reconstruction is based on the precipitation of the redox sensitive metal uranium as a proxy for deep water oxygen concentrations. Because any change in oceanic storage of respiratory carbon must be accompanied by corresponding changes in dissolved oxygen concentrations, data reflecting bottom water oxygenation are of value in addressing questions of glacial carbon sequestration. The record reveals periods of deep ocean aU deposition during each of the last three glacial maxima. Export productivity data indicate these intervals are not associated with local productivity increases, indicating episodic precipitation of aU occurs in response to basin-wide decreases in deep water oxygen concentrations. Not only does the aU record show the history of dissolved oxygen concentrations in the central equatorial Pacific, it also provides an opportunity for the reconciliation of records previously interpreted as incompatible with one another and with the storage of respired carbon. Synthesis of existing data suggests the existence of a ’floating’ pool of respired carbon between 2 and 3.5 km depth in the equatorial Pacific. This hypothesis permits the interpretation of existing proxy data reflecting abyssal LGM circulation and carbon storage without invoking a glacial watermass geometry significantly different from present. The new data and conclusions presented in Chapter 4 represent a significant advance in our understanding of where carbon was stored in the ocean during successive glacial periods. The perspective provided by the new aU time series is spatiotemporally unique and constitutes compelling evidence that hypotheses of marine carbon storage developed to explain the last glacial period are equally applicable to previous Pleistocene glacial periods. The three studies presented in this thesis provide strong support for the utility of U and Th series isotopes in paleoenvironmental reconstructions. Not only does this work demonstrate the range of paleoclimatic proxy data that can be obtained from isotopes of U and Th, it also illustrates the value of interpretations derived from their analysis. The records presented here represent a substantial contribution to our knowledge of marine hydroclimate and ocean circulation over the last 350 kyr and motivate additional high resolution paleoclimate work using isotopes of U and Th.

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a delta Cl-37 range of 0 +/- 3 parts per thousand, far greater than the range for marine evaporites. Basins characterized by high positive (-1 to +3 parts per thousand), near-0%, and negative (-0.3 to -2.6%) are documented. Halite in weathered crusts of sedimentary rocks has delta Cl-37 values as high as +5.6 parts per thousand. Salt-excluding halophyte plants excrete salt with a delta Cl-37 range of -2.1 to -0.8%. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of delta Cl-37. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive delta Cl-37 values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1-10 cm can produce high delta Cl-37 values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative delta Cl-37 values in certain situations; such may explain halite deposits with bulk negative delta Cl-37 values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.