In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS-determined mean U-Pb radiogenic isotopic ratios of 0.084743 +/- 0.000027 for Pb-206/U-238 and 0.67676 +/- 0.00023 for Pb-207/U-235 (weighted means, 2s uncertainties). Its Pb-206/U-238 age of 524.36 +/- 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The delta O-18 value (determined by laser fluorination) is 8.26 +/- 0.06 parts per thousand VSMOW (2s), and the mean Hf-176/Hf-177 ratio (determined by solution ICP-MS) is 0.282396 +/- 0.000004 (2s). The SIMS-determined delta Li-7 value is -0.6 +/- 0.9 parts per thousand (2s), with a mean mass fraction of 1.0 +/- 0.1 mu g g(-1) Li (2s). Zircon M127 contains similar to 923 mu g g(-1) U. The moderate degree of radiation damage corresponds well with the time-integrated self-irradiation dose of 1.82 x 10(18) alpha events per gram. This observation, and the (U-Th)/He age of 426 +/- 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U-Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.

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The research presented here is an effort to characterize changes in marine oxygen availability across a portion of the later Cambrian noted for unique evolutionary dynamics and which includes a significant global oceanographic event known as the SPICE event (Steptoean Positive Carbon Isotope Excursion). Previous studies have revealed the SPICE caused large changes to the global cycles of carbon, sulfur, uranium, molybdenum and the overall trace metal content of seawater. Furthermore, the initiation of these changes appears to have been temporally coupled with marine extinctions across several paleocontinents raising the possibility of a common causal linkage between all these features. In particular, expanding marine anoxia has been invoked as the most parsimonious explanation for these co-occurring features. The research presented here tests this hypothesis directly across a range of spatial scales using the iron speciation paleoredox proxy to characterize redox conditions within individual basins and to facilitate comparison of conditions between basins. In addition to these analyses, we apply a new proxy, thallium stable isotopes to this interval to assess potential global changes in deoxygenation across the event. These iron speciation analyses showed shallow environments deoxygenated coincident with the initiation of the SPICE and extinction horizons, and these conditions were dominantly ferruginous. Importantly, this work also shows deeper-water environments were deoxygenated prior to and remained so across the event and these environments were also largely. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation would be recorded as a positive shift across the interval if expanded anoxia were to impact the areal extent of manganese-oxide sedimentation and burial. We found it did record these changes, but with a different expression than during other more recent events explored using the isotope system. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which as documented herein were widely oxygen-deficient in their deeper depths. Given this recognition we suggest that thallium isotope studies in deep time should account for this redox structure of ancient oceans likely common under the less-oxygenated atmospheres of the ancient Earth. / Doctor of Philosophy / The research presented here is a story about oxygen in the oceans during an ancient portion of Earth history within the Cambrian Period (around 500 million years ago), soon after animal life first appears in the geologic record. The emerging biosphere of this time seems to have been particularly prone to extinctions, leading to the idea that environmental conditions, such as oxygen availability at the seafloor created difficult circumstances for animals in these ancient seas. This work seeks to quantify the levels of marine oxygenation at this time, however this remains a fundamental challenge because they cannot be directly measured from the rocks we study. Therefore, we rely on how the presence or absence of oxygen changed the chemistry of these rocks at the time they were sediments deposited on the seafloor. Here we use the behavior of two different elements, iron (Fe) and thallium (Tl), to understand changes in oxygen in the oceans around a large, globally-recorded extinction event called the SPICE event. Studying how much iron is concentrated in certain minerals in the rocks formed during this event allowed us to track how changes in oxygen may relate to these notable extinctions. We found that shallow coastal areas changed from oxygenated to deoxygenated at the same time of the extinctions, suggesting a direct role for this environmental shift in the biological crisis. Furthermore, we compared other locations from around the world using more new iron measurements in conjunction with previously published ones compiled by a collaborative geochemistry database project. This work revealed the deeper oceans were deoxygenated prior to and across the SPICE event and that the decline in oxygen in shallower environments was where most environmental change occurred during this time. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation changed its global cycle. We found it did record global changes, but they were expressed differently than during other more recent events that have been studied. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which were widely oxygen-deficient in their deeper depths.

Le présent travail porte sur le développement technologique pour déterminer l'âge des sources de radiostrontium à travers du rapport [Zr-90]/[Sr-90], en utilisant les techniques de spectrométrie de masse et scintillation liquide pour quantifier les deux isotopes. Parce que Sr-90 et Zr-90 sont des interférences isobariques en spectrométrie de masse, une séparation radiochimique est nécessaire pour isoler du Zr-90 avant son analyse. Parmi quatre résines commerciales, la résine DGA a fourni la meilleure performance pour isoler le Zr-90 du Sr-90. Des récupérations supérieures à 99% pour le Zr-90 ont été obtenues. La résine DGA était aussi l'approche la plus rapide et la plus efficace pour éliminer les interférences isobariques du Sr-90 et aussi de l’Y-90 potentiellement présents dans des échantillons contenant des niveaux élevés de radioactivité. Des expériences impliquant l’utilisation d’une cellule de collision pour éliminer des interférences isobariques ont fourni des facteurs de décontamination insuffisants pour des applications en criminalistique nucléaire. / In this work, a technological development to determine the age of radioactive strontium sources through the [Zr-90]/[Sr-90] ratio using mass spectrometry and liquid scintillation to quantify both isotopes is presented. Because Sr-90 and Zr-90 are isobaric interferences in mass spectrometry, a radiochemical separation to isolate Zr-90 has been shown to be mandatory prior to analysis. Four commercial resins (AG50W-X9, Dowex1-X8, Sr and DGA resins) were tested to isolate Zr-90 from Sr-90. Best performance was observed for the DGA resin, including recoveries higher than 99% for Zr-90. DGA has also demonstrated to be the faster approach and the most efficient not only to eliminate isobaric interferences from Sr-90, but also from Y-90, potentially present in samples containing high levels of radioactivity. Experiments using a collision cell to eliminate isobaric interferences in a triple quadrupole mass spectrometer (ICP-QQQMS) have also been carried out, but results have demonstrated insufficient decontamination factors for nuclear forensic applications.

La lithosphère continentale est physiquement et chimiquement segmentée. La cartographie des isotopes radiogéniques de roches plutoniques acides, représentatives de la croûte continentale, et de laves basiques, représentatives du manteau, possède des similarités avec la cartographie sismique de la lithosphère sous-jacente. Ces similitudes permettent d’interpréter les observations sismiques en étudiant leurs caractéristiques chimiques et leur âge. Les isotopes du plomb permettent de dater et d’identifier l’empilement de segments crustaux qui forment la croûte. L’écart des âges modèles du plomb avec d’autres systèmes identifie le recyclage crustal et le réchauffement de la croûte au dessus de la température du système plomb-plomb. Le système plomb-plomb donne également accès au sous-étudié rapport Th/U qui contraint la profondeur de la source des roches continentales. Certains échantillons de l’ouest U.S.A. proviennent de la croute inférieure, et se sont formés par l’extension crustale ou par un flux de matériel au sein de la croûte. Les isotopes du néodyme et de l’hafnium marquent la fusion du manteau lithosphérique enrichis sous le Colorado Plateau, une région où est observée le détachement du manteau lithosphérique sub-continental. Ce manteau fond par décompression adiabatique, par extension localisée ou remontée asthénosphérique engendrée par la convection locale. Au final, l’association des systèmes isotopiques du plomb, du néodyme, et de l’hafnium avec la sismologie est une approche puissante pour étudier la formation et la déformation de la lithosphère continentale. / Continental lithosphere is physically and chemically segmented. The mapping at a continent size scale of radiogenic isotopes from plutonic acid rocks, sampling the continental crust, and from mafic lavas, sampling the mantle, has similarities with the seismic mapping of the underlying lithosphere. These similarities allow to interpret the seismic observations by studying their chemical characteristics and age. Lead isotopes are used to date and identify the stacking of crustal segments that form the crust. The deviation of Lead model ages with other system is used to identify crustal recycling and the heating of the crust above the Lead-Lead system closing temperature. The Lead-Lead system also give access to the under-studied Th/U ratio that constrains the depth of the continental rock sources. Somes samples from the Western U.S. are coming from the lower crust, formed by crustal extension or crustal flowing within the crust. Neodymium and Hafnium isotopes identify the fusion of an enriched lithospheric mantle under the Colorado Plateau, a place where lithospheric delamination has been observed. This mantle melts by adiabatic decompression due to localized expansion or asthenospheric upwelling caused by secondary convection. At the end, the merging of Lead, Neodymium, and Hafnium isotopic systems with seismology is a powerful tool to study the formation and deformation of the continental lithosphere.

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Typescript (photocopy). / Digitized by Kansas Correctional Industries